Pyridinyl amides and compositions thereof for use as fungicides

ABSTRACT

Compositions for controlling plant diseases caused by fungal plant pathogens are described, comprising: (a) at least one compound of Formula I, including all geometric and stereoisomers, N-oxides and agriculturally suitable salts thereof: (I) wherein R 1 , R 2 , R 5  and R 6 , m and n are as defined in the disclosure, and (b) at least one compound selected from the group consisting of (b1) alkylenebis(dithiocarbamate) fungicides; (b2) compounds acting at the bc 1  complex of the fungal mitochondrial respiratory electron transfer site, (b3) cymoxanil, (b4) compounds acting at the demethylase enzyme of the sterol biosynthesis pathway; (b5) morpholine and piperidine compounds that act on the sterol-biosynthesis pathway; (b6) phenylamide fungicides; (b7) pyrimidinone fungicides; (b8) phthalimides; and (b9) fosetyl-aluminum. Also disclosed are methods for controlling plant diseases caused by fungal plant pathogens that involves applying an effective amount of the combinations described. Also disclosed are certain novel compounds of Formula I.

BACKGROUND OF THE INVENTION

This invention relates to certain pyridinyl amides, their N-oxides,agriculturally suitable salts, certain advantageous compositionscontaining a mixture of pyridinyl amides and other fungicides andmethods of their use as fungicides.

The control of plant diseases caused by fungal plant pathogens isextremely important in achieving high crop efficiency. Plant diseasedamage to ornamental, vegetable, field, cereal, and fruit crops cancause significant reduction in productivity and thereby result inincreased costs to the consumer. Many products are commerciallyavailable for these purposes, but the need continues for new productsthat are more effective, less costly, less toxic, or environmentallysafer.

WO 01/11966 discloses certain pyridinyl amides of formula i asfungicides

-   -   wherein, among others,    -   A¹ is 2-pyridyl substituted by up to four groups at least one of        which is haloalkyl;    -   A² is optionally substitted heterocyclyl;    -   R¹ and R² are independently H, alkyl or acyl;    -   R³ is H or alkyl; and    -   L is —(C═O)—, —SO₂— or —(C═S)—.

Fungicides that effectively control plant fungi, particularly of theclass Oomycetes, such as Phytophthora spp. and Plasmopara spp., are inconstant demand by growers. Combinations of fungicides are often used tofacilitate disease control and to retard resistance development. It isdesirable to enhance the activity spectrum and the efficacy of diseasecontrol by using mixtures of active ingredients that provide acombination of curative, systemic and preventative control of plantpathogens. Also desirable are combinations that provide greater residualcontrol to allow for extended spray intervals. It is also very desirableto combine fungicidal agents that inhibit different biochemical pathwaysin the fungal pathogens to retard development of resistance to any oneparticular plant disease control agent.

It is in all cases particularly advantageous to be able to decrease thequantity of chemical agents released in the environment while ensuringeffective protection of crops from diseases caused by plant pathogens.Mixtures of fungicides may provide significantly better disease controlthan could be predicted based on the activity of the individualcomponents. This synergism has been described as “the cooperative actionof two components of a mixture, such that the total effect is greater ormore prolonged than the sum of the effects of the two (or more) takenindependently” (see Tames, P. M. L., Neth. J. Plant Pathology, (1964),70, 73-80).

There is a desire to find fungicidal agents that are particularlyadvantageous in achieving one or more of the preceding objectives.

SUMMARY OF THE INVENTION

This invention provides a composition for controlling plant diseasescaused by fungal plant pathogens comprising (a) at least one compound ofFormula I (including all geometric and stereoisomers), N-oxides andagriculturally suitable salts thereof:

wherein

-   -   R¹ and R² are each independently H or C₁-C₆ alkyl;    -   each R⁵ is independently C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆        alkynyl, C₃-C₆ cycloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl,        C₃-C₆ halocycloalkyl, halogen, CN, CO₂H, CONH₂, NO₂, hydroxy,        C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄        alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylthio, C₁-C₄        haloalkylsulfinyl, C₁-C₄ haloalkylsulfonyl, C₁-C₄ alkylamino,        C₂-Cg dialkylamino, C₃-C₆ cycloalkylamino, C₂-C₆ alkylcarbonyl,        C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl, C₃-C₈        dialkylaminocarbonyl or C₃-C₆ trialkylsilyl;    -   each R⁶ is independently C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆        alkynyl, C₃-C₆ cycloalkyl C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl        C₂-C₆ haloalkynyl, C₃-C₆ halocycloalkyl, halogen, CN, CO₂H,        CONH₂, NO₂, hydroxy, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄        alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄        haloalkylthio, C₁-C₄ haloalkylsulfinyl, C₁-C₄ haloalkylsulfonyl,        C₁-C₄ alkylamino, C₂-C₈ dialkylamino, C₃-C₆ cycloalkylamino,        C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆        alkylaminocarbonyl, C₃-C₈ dialkylaminocarbonyl, C₃-C₆        trialkylsilyl; and

-   m and n are independently 1, 2, 3 or 4; and    -   (b) at least one compound selected from the group consisting of    -   (b1) alkylenebis(dithiocarbamate) fungicides;    -   (b2) compounds acting at the bc₁ complex of the fungal        mitochondrial respiratory electron transfer site;    -   (b3) cymoxanil;    -   (b4) compounds acting at the demethylase enzyme of the sterol        biosynthesis pathway;    -   (b5) morpholine and piperidine compounds that act on the sterol        biosynthesis pathway;    -   (b6) phenylamide fungicides;    -   (b7) pyrimidinone fungicides;    -   (b8) phthalimides; and    -   (b9) fosetyl-aluminum

This invention also relates to compounds of Formula I wherein at leastone R⁶ is iodo.

This invention also relates to a method for controlling plant diseasescaused by fungal plant pathogens comprising applying to the plant orportion thereof, or to the plant seed or seedling, a fungicidallyeffective amount of a compound or composition of the invention.

DETAILS OF THE INVENTION

In the above recitations, the term “alkyl”, used either alone or incompound words such as “alkylthio” or “haloalkyl” includesstraight-chain or branched alkyl, such as, methyl ethyl, n-propyl,i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl”includes straight chain or branched alkenes such as ethenyl, 1-propenyl,2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.“Alkenyl” also includes polyenes such as 1,2-propadienyl and2,4-bexadienyl. “Alkynyl” includes straight chain or branched alkynessuch as ethynyl, 1-propynyl, 2-propynyl and the different butynyl,pentynyl and hexynyl isomers. “Alkynyl” can also include moietiescomprised of multiple triple bonds such as 2,5-hexadiynyl. “Alkoxy”includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy andthe different butoxy, pentoxy and hexyloxy isomers. “Alkoxyalkyl”denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” includeCH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂ andCH₃CH₂OCH₂CH₂“Alkoxyalkoxy” denotes alkoxy substitution on alkoxy. Theterm “Alkenyloxy” includes straight chain or branched alkenyloxymoieties. Examples of “alkenyloxy” include H₂C═CHCH₂O, (CH₃)₂C═CHCH₂O,(CH₃)CH═CHCH₂O, (CH₃)CH═C(CH₃)CH₂O and CH₂═CHCH₂CH₂O. “Alkynyloxy”includes straight chain or branched alkynyloxy moieties. Examples of“alkynyloxy” include HC≡CCH₂O, CH₃C═CCH₂O and CH₃C≡CCH₂CH₂O. “Alkylthio”includes branched or straight chain alkylthio moieties such asmethylthio, ethylthio, and the different propylthio, butylthio,pentylthio and hexylthio isomers. “Alkylthioalkyl” denotes alkylthiosubstitution on alkyl. Examples of “alkylthioalkyl” include CH₃SCH₂,CH₃SCH₂CH₂, CH₃CH₂SCH₂, CH₃CH₂CH₂CH₂SCH₂ and CH₃CH₂SCH₂CH₂.“Alkylthioalkoxy” denotes alkylthio substitution on alkoxy.“Alkylsulfinyl” includes both enantiomers of an alkylsulfinyl group.Examples of “alkylsulfinyl” include CH₃S(O), CH₃CH₂S(O), CH₃CH₂CH₂S(O),(CH₃)₂CHS(O) and the different butylsulfinyl, pentylsulfinyl andhexylsulfinyl isomers. Examples of “alkylsulfonyl” include CH₃S(O)₂,CH₃CH₂S(O)₂, CH₃CH₂CH₂S(O)₂, (CH₃)₂CHS(O)₂ and the differentbutylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. “Alkylamino”,“dialkylamino”, “alkenylthio”, “alkenylsulfinyl”, “alkenylsulfonyl”,“alkynylthio”, “alkynylsulfinyl”, “alkynylsulfonyl”, and the like, aredefined analogously to the above examples. “Cycloalkyl” includes, forexample, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term“cycloalkoxy” includes the same groups linked through an oxygen atomsuch as cyclopentyloxy and cyclohexyloxy.

The term “halogen”, either alone or in compound words such as“haloalkyl”, includes fluorine, chlorine, bromine or iodine. Further,when used in compound words such as “haloalkyl”, said alkyl may bepartially or fully substituted with halogen atoms which may be the sameor different. Examples of “haloalkyl” include F₃C, ClCH₂, CF₃CH₂ andCF₃CCl₂. The terms “haloalkenyl”, “haloalkynyl”, “haloalkoxy”,“haloalkylthio”, and the like, are defined analogously to the term“haloalkyl”. Examples of “haloalkenyl” include (Cl)₂C═CHCH₂ andCF₃CH₂CH═CHCH₂. Examples of “haloalkynyl” include HC≡CCHCl, CF₃C≡C,CCl₃C≡C and FCH₂C≡CCH₂. Examples of “haloalkoxy” include CF₃O, CCl₃CH₂O,HCF₂CH₂CH₂O and CF₃CH₂O. Examples of “haloalkylthio” include CCl₃S,CF₃S, CCl₃CH₂S and ClCH₂CH₂CH₂S. Examples of “haloalkylsulfinyl” includeCF₃S(O), CCl₃S(O), CF₃CH₂S(O) and CF₃CF₂S(O). Examples of“haloalkylsulfonyl” include CF₃S(O)₂, CCl₃S(O)₂, CF₃CH₂S(O)₂ andCF₃CF₂S(O)₂. Examples of “haloalkoxyalkoxy” include CF₃OCH₂O,ClCH₂CH₂OCH₂CH₂O, Cl₃CCH₂OCH₂O as well as branched alkyl derivatives.Examples of “alkylcarbonyl” include C(O)CH₃, C(O)CH₂CH₂CH₃ andC(O)CH(CH₃)₂. Examples of “alkoxycarbonyl” include CH₃C(═O),CH₃CH₂C(═O), CH₃CH₂CH₂C(═O), (CH₃)₂CHOC(═O) and the different butoxy- orpentoxycarbonyl isomers.

One skilled in the art will appreciate that not all nitrogen containingheterocycles can form N-oxides since the nitrogen requires an availablelone pair for oxidation to the oxide; one skilled in the art willrecognize those nitrogen containing heterocycles which can formN-oxides. One skilled in the art will also recognize that tertiaryamines can form N-oxides. Synthetic methods for the preparation ofN-oxides of heterocycles and tertiary amines are very well known by oneskilled in the art including the oxidation of heterocycles and tertiaryamines with peroxy acids such as peracetic and m-chloroperbenzoic acid(MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butylhydroperoxide, sodium perborate, and dioxiranes such asdimethydioxirane. These methods for the preparation of N-oxides havebeen extensively described and reviewed in the literature, see forexample: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik inComprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boultonand A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keenein Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R.Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advancesin Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzlcy and A.J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G.Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A.R. Katritzky and A. J. Boulton, Eds., Academic Press.

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 8. Forexample, C₁-C₃ alkylsulfonyl designates methylsulfonyl throughpropylsulfonyl; C₂ alkoxyalkyl designates CH₃OCH₂; C₃ alkoxyalkyldesignates, for example, CH₃CH(OCH₃), CH₃OCH₂CH₂ or CH₃CH₂OCH₂; and C₄alkoxyalkyl designates the various isomers of an alkyl group substitutedwith an alkoxy group containing a total of four carbon atoms, examplesincluding CH₃CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂.

When a compound is substituted with a substituent bearing a subscriptthat indicates the number of said substituents can exceed 1, saidsubstituents (when they exceed 1) are independently selected from thegroup of defined substituents. Further, when the subscript indicates arange, e.g. (R)_(i-j), then the number of substituents may be selectedfrom the integers between i and j inclusive. The term “optionallysubstituted with one to three substituents” and the like indicates thatone to three of the available positions on the group may be substituted.

When a group contains a substituent which can be hydrogen, for exampleR¹ or R² then, when this substituent is taken as hydrogen, it isrecognized that this is equivalent to said group being unsubstituted.

Compounds of Formula I can exist as one or more stereoisomers. Thevarious stereoisomers include enantiomers, diastereomers, atropisomersand geometric isomers. One skilled in the art will appreciate that onestereoisomer may be more active and/or may exhibit beneficial effectswhen enriched relative to the other stereoisomer(s) or when separatedfrom the other stereoisomer(s). Additionally, the skilled artisan knowshow to separate, enrich, and/or to selectively prepare saidstereoisomers. Accordingly, the present invention comprises compoundsselected from Formula I, N-oxides and agriculturally suitable saltsthereof. The compounds of Formula I may be present as a mixture ofstereoisomers, individual stereoisomers, or as an optically active form.In particular, when R¹ and R² of Formula I are different, then saidFormula possesses a chiral center at the carbon to which R¹ and R² arecommonly bonded.

This invention includes racemic mixtures of equal parts of Formula I′and Formula I″.

-   -   wherein A is a 2-pyridinyl group substituted with (R⁵)_(m) and B        is a 3-pyridinyl group substituted with (R⁶)_(n), and R⁵, R⁶, m        and n are as defined above.

In addition, this invention includes compounds and compositions that areenriched compared to the racemic mixture in an enantiomer of the FormulaI′ or Formula I″. Included are compounds and compositions involving theessentially pure enantiomers of Formula I′ or Formula I″. For example,this invention also includes compounds of Formula I wherein at least oneR⁶ is iodo that are enriched compared to the racemic mixture in anenantiomer of the Formula I′. Included are the essentially pureenantiomers of Formula I′. This invention also includes compositionswherein component (a) is enriched in a component (a) enantiomer ofFormula I′ compared to the racemic mixture. This invention also includescompounds of Formula I wherein at least one R⁶ is iodo that are enrichedcompared to the racemic mixture in an enantiomer of the Formula I″.Included are the essentially pure enantiomers of Formula I″. Thisinvention also includes compositions wherein component (a) is enrichedin a component (a) enantiomer of Formula I″ compared to the racemicmixture.

When enantiomerically enriched, one enantiomer is present in greateramounts that the other and the extent of enrichment can be defined by anexpression of enantiomer excess(“ee”), which is defined as 100(2x−1)where x is the mole fraction of the dominant enantiomer in theenantiomer mixture (e.g., an ee of 20% corresponds to a 60:40 ratio ofenantiomers).

The more active enantiomer with respect to the relative positions of R¹,R², A and the rest of the molecule bonded through nitrogen correspondsto the configuration of the enantiomer that, when in a solution ofCDCl₃, rotates plane polarized light in the (+) or dextro direction.

Preferably there is at least a 50% enantiomeric excess; more preferablyat least a 75% enantiomeric excess; still more preferably at least a 90%enantiomeric excess; and the most preferably at least a 94% enantiomericexcess of the more active isomer of Formula I. Of particular note areenantiomerically pure embodiments of the more active isomer of FormulaI.

The salts of the compounds of Formula I include acid-addition salts withinorganic or organic acids such as hydrobromic, hydrochloric, nitric,phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic,oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valericacids. The salts of the compounds of Formula I also include those formedwith organic bases (e.g., pyridine, ammonia, or triethylamine) orinorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium,potassium, lithium, calcium, magnesium or barium) when the compoundcontains an acidic group such as a carboxylic acid or phenol.

Preferred compositions of the invention, wherein (a) comprises compoundsof Formula I, for reasons of better activity and/or ease of synthesisare:

-   Preferred 1. Preferred are compositions wherein in Formula I at    least one R⁶ located in a position ortho to the link with C═O.-   Preferred 2. Compositions of Preferred 1 wherein there is an R⁶ at    each position ortho to the link with C═O, and optionally 1 to 2    additional R⁶ and R⁶ is either halogen or methyl.-   Of note are compositions wherein at least one R⁶ is iodo.-   Preferred 3. Compositions of Preferred 2 wherein one R⁶ is a Cl    located at the 2-position ortho to the link with C═O, another R⁶ is    selected from Cl or methyl and is located at the 4-position ortho to    the link with C═O and a third optional R⁶ is methyl at the    6-position.

Of note are compounds of Formula I wherein R⁵ is Cl, Br, I, CH₃, OCF₃,OCHF₂, OCH₂CF₃, OCF₂CF₃, OCF₂CF₂H, OCHFCF₃, SCF₃, SCHF₂, SCH₂CF₃,SCF₂CF₃, SCF₂CF₂H, SCHFCF₃, SOCF₃, SOCHF₂, SOCH₂CF₃, SOCF₂CF₃,SOCF₂CF₂H, SOCHFCF₃, SO₂CF₃, SO₂CHF₂, SO₂CH₂CF₃, SO₂CF₂CF₃, SO₂CF₂CF₂Hor SO₂CHFCF₃.

Preferred compositions of this invention include those of Preferred 1through Preferred 3 wherein in Formula I one R⁵ is halogen at the3-position and a second R⁵ is halogen or C₁-C₆ haloalkoxy at the5-position. Of note are compositions comprising compounds of Formula Ithat are substituted with at least one iodo as R⁵.

Preferred compositions of this invention include those of Preferred Ithrough Preferred 3 wherein R¹ is H and R² is H or CH₃. More preferredare compositions of Preferred 1 through Preferred 3 wherein R¹ is H andR² is CH₃.

Specifically preferred are compositions comprising a compound selectedfrom the group consisting of

-   2,4-Dichloro-N-[(3,5-dichloro-2-pyridinyl)methyl]-3-pyridinecarboxamide,-   2,4-Dichloro-N-[1-(3,5-dichloro-2-pyridinyl)ethyl]-3-pyridinecarboxamide,-   2,4-Dichloro-N-[(3,5-dichloro-2-pyridinyl)methyl]-6-methyl-3-pyridinecarboxamide,-   2,4-Dichloro-N-[1-(3,5-dichloro-2-pyridinyl)ethyl]-6-methyl-3-pyridinecarboxamide,-   N-[(5-bromo-3-chloro-2-pyridinyl)methyl]-2,4-dichloro-3-pyridinecarboxamide,-   N-[1-(5-bromo-3-chloro-2-pyridinyl)ethyl]-2,4-dichloro-3-pyridinecarboxamide,-   N-[(5-bromo-3-chloro-2-pyridinyl)methyl]-2,4-dichloro-6-methyl-3-pyridinecarboxamide,-   N-[1-(3-chloro-5-iodo-2-pyridinyl)ethyl]-2,4-dichloro-6-methyl-3-pyridinecarboxamide,-   N-[(3-chloro-5-iodo-2-pyridinyl)methyl]-2,4-dichloro-3-pyridinecarboxamide,-   N-[1-(3-chloro-5-iodo-2-pyridinyl)ethyl]-2,4-dichloro-3-pyridinecarboxamide,-   N-[(3-chloro-5-iodo-2-pyridinyl)methyl]-2,4-dichloro-6-methyl-3-pyridinecarboxamide,    and-   N-[1-(3-chloro-5-iodo-2-pyridinyl)ethyl]-2,4-dichloro-6-methyl-3-pyridinecarboxamide.

This invention also relates to a method for controlling plant diseasescaused by fungal plant pathogens comprising applying to the plant orportion thereof, or to the plant seed or seedling, a fungicidallyeffective amount of the composition of the invention (i.e., as acomposition described herein). The preferred methods of use are thoseinvolving the above-preferred compositions.

The compounds of Formula I can be prepared by one or more of thefollowing methods and variations as described in Schemes 1-5. Thedefinitions of A, B, R¹ through R⁶ and n in the compounds of Formulas1-4 below are as defined above. Compounds of Formula 1a, 1b and 1c aresubsets of Formula 1. Compounds of Formulae Ia, Ib and Ic are subsets ofthe compounds of Formula 1, and all substituents for Formulae Ia, Ib andIc are as defined above for Formula I.

As shown in Scheme 1, the compounds of Formula Ia can be prepared bytreating amine salts of Formula 1 with an appropriate acid chloride inan inert solvent with two molar equivalents of a base (e.g.triethylamine or potassium carbonate) present. Suitable solvents areselected from the group consisting of ethers such as tetrahydrofuran,dimethoxyethane, or diethyl ether; hydrocarbons such as toluene orbenzene; and halocarbons such as dichloromethane or chloroform.

As depicted in Scheme 2, compounds of Formula Ia can be alternativelysynthesized by reacting the amine salts of Formula 1 with an appropriatecarboxylic acid in the presence of an organic dehydrating reagent suchas 1,3-dicyclohexylcarbodiimide (DCC) or1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (EDC).Suitable solvents are selected from the group consisting of ethers suchas tetrahydrofuran, dimethoxyethane, or diethyl ether; hydrocarbons suchas toluene or benzene; and halocarbons such as dichloromethane orchloroform.

As shown in Scheme 3, the amine salts of Formula 1a, wherein A is2-pyridyl bearing the indicated substituents and R¹ and R² are hydrogen,can be prepared by reacting the commercially available imine ester 5with a 2,3-dichloro-pyridine of Formula 4 in the presence of a strongbase such as sodium hydride in a polar, aprotic solvent such asN,N-dimethylformamide followed by heating in acidic medium in aprocedure analogous to those found in WO99/42447. Compounds of Formula1b can be prepared by similar procedures in which the intermediate anionresulting from step 1 is treated with an alkylating agent R²—X such asmethyl iodide prior to beating in an acidic medium. In the alkylatingreagent R²—X, X is a suitable leaving group such as halogen (e.g., Br,I), OS(O)₂CH₃ (methanesulfonate), OS(O)₂CF₃, OS(O)₂Ph-p-CH₃(p-toluenesulfonate), and the like; methanesulfonate works well. Of noteare compounds of 1a, 1b and 4 wherein R⁵ is CF₃.

As shown in Scheme 4, compounds of Formula 1c (wherein A is asubstituted 2-pyridinyl ring), bearing an aminomethyl group, can besynthesized from nitriles of Formula 2 (wherein A is a substituted2-pyridinyl ring) by reduction of the nitrile using lithium aluminumhydride (LAH) in toluene.

A is a substituted 2-pyridinyl ring

As shown in Scheme 5, compounds of Formula 1c (wherein A is asubstituted 2-pyridinyl ring) can be alternatively synthesized byreacting compounds of Formula 3 with ammonia in a protic solvent such asmethanol to provide compounds of Formula 1c. Compounds of Formula 1c canalso be prepared by reacting compounds of Formula 3 with a potassiumsalt of phthalimide followed by reaction with either aminoethanol orhydrazine in an alcohol solvent to provide the desired aminomethylintermediates of Formula 1c.

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula I may not be compatible withcertain functionalities present in the intermediates. In theseinstances, the incorporation of protection/deprotection sequences orfunctional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after the introduction of a given reagentas it is depicted in any individual scheme, it may be necessary toperform additional routine synthetic steps not described in detail tocomplete the synthesis of compounds of Formula I. One skilled in the artwill also recognize that it may be necessary to perform a combination ofthe steps illustrated in the above schemes in an order other than thatimplied by the particular sequence presented to prepare the compounds ofFormula I.

One skilled in the art will also recognize that compounds of Formula Iand the intermediates described herein can be subjected to variouselectrophilic, nucleophilic, radical, organometallic, oxidation, andreduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can prepare compounds comprisingcomponent (a) of the present invention to its fullest extent. Thefollowing Examples are, therefore, to be construed as merelyillustrative, and not limiting of the disclosure in any way whatsoever.Percentages are by weight except for chromatographic solvent mixtures orwhere otherwise indicated. Parts and percentages for chromatographicsolvent mixtures are by volume unless otherwise indicated. ¹H NMRspectra are reported in ppm downfield from tetramethylsilane; s issinglet, d is doublet, t is triplet, q is quartet, m is multiplet, dd isdoublet of doublets, dt is doublet of triplets, br s is broad singlet.

EXAMPLE 1 Preparation ofN-[1-(5-bromo-3-chloro-2-pyridinyl)ethyl]-2,4-dichloro-3-pyridinecarboxamide

Step A: Preparation of 5-bromo-3-chloro-2(1H)-pyridone

A solution of 6.2 g of potassium chlorate in 100 mL of water was addedto a solution of 25 g of 5-bromo-2-pyridone in 100 mL concentrated HClpre-heated to 50° C. to 60° C. to form a thick precipitate that wasstirred for 5 min. Then, 60 mL of water was added to facilitate stirringand the mixture was stirred at room temperature overnight. The reactionmixture was filtered, triturated with water (2×), and the precipitatewas suction-dried to yield 17.7 g of the title compound as a solid.

¹H NMR (CDCl₃): δ 7.53 (d, 1H, J is 2.6 Hz), 7.75 (d, 1H, J is 2.5 Hz)

Step B: Preparation of 5-bromo-2.3-dichloropyridine

A mixture of 5-bromo-3-chloro-2(1H)-pyridone (i.e. the product of StepA) (17.7 g), PCl₅ (10 g) in 100 mL POCl₃ was refluxed for 4 hours withscrubbing. The reaction mixture was concentrated under reduced pressureto remove most of the POCl₃, carefully poured into warm water, cooled toroom temperature and then extracted with methylene chloride (2×). Thecombined extracts were dried over magnesium sulfate and concentrated togive an oil which was subjected to column chromatography(8:2/hexanes:ethyl acetate) to give 4.2 g of the title compound as anoil.

¹H NMR (CDCl₃): δ 7.94(d, 1H, J is 2.2 Hz), 8.37(d, 1H, J is 2.3 Hz).

Step C: Preparation of 5-Bromo-3-chloro-α-methyl-2-pyridinemethanaminehydrochloride

5-Bromo-2,3-dichloropyridine (i.e. the product of Step B) (4.1 g) wasadded to a suspension of sodium hydride (60% oil suspension) in 30 mL ofdry N,N-dimethylformamide at 0° C. under nitrogen.N-(Diphenylmethylene)glycine ethyl ester (4.6 g) was added in portionswith no exotherm, and the mixture was stirred at room temperature for 3hours. Then, 3.4 mL of methyl iodide was added at <30° C. and thereaction mixture was stirred overnight at room temperature. The reactionmixture was diluted with water and extracted with diethyl ether (2×).The combined extracts were washed with saturated brine (1×) andconcentrated to an oil that was then refluxed in 50 mL of 12N HCl for 4hours. The reaction mixture was concentrated to an oil, cooled, andslurried with diethyl ether overnight. The ether was then decanted offand the residue was dried in a vacuum oven to give 1.3 g of the titlecompound as a solid.

¹H NMR (CDCl₃): 1.40 and 1.46(dd, 3H, J is 7.0 Hz), 4.7(m, 1H), 8.48(d,1H J is 1.8), 8.6(bs, 3H), 8.79(d, 1H, J is 1.9 Hz).

Step D: Preparation ofN-[1-(5-bromo-3-chloro-2-pyridinyl)ethyl]-2,4-dichloro-3-pyridinecarboxamide

A mixture of 5-bromo-3-chloro-α-methyl-2-pyridinemethanaminehydrochloride (i.e the product of Step C) (0.80 g), triethyl amine (1.21mL) and 2,4-dichloronicotinoyl chloride (0.62 g) in 25 mL of methylenechloride was stirred at room temperature overnight. The reaction mixturewas concentrated to produce the title compound, a compound of thepresent invention, as a solid.

¹H NMR (CDCl₃): δ 1.59(d, 3H, J is 6.6 Hz), 5.75(m, 1H), 7.3(bs, 1H),7.34(d, 1H, J is 5.2 Hz), 7.91(d, 1H, J is 1.9 Hz), 8.33(d, 1H, J is 5.4Hz), 8.49(d, 1H, J is 1.9 Hz).

EXAMPLE 2 Preparation of2,4-Dichloro-Ar-[1-(3,5-dichloro-2-pyridinyl)ethyl]-3-pyridinecarboxamide

Example 2 was prepared in analogous fashion to Example 1 using2-bromo-3,5-dichloropyridine as the starting material and subjectingthis material to conditions analogous to those described in Steps C (toprepare 3,5-dichloro-α-methyl-2-pyridinemethanamine) and D of Example 1to give the title compound as a solid.

¹H NMR (CDCl₃): δ 1.58(d, 3H, J is 6.6 Hz), 5.7-5.8(m, 1H), 7.4(m, 2H),7.77(m, 1H), 8.35(m, 1H), 8.40(m, 1H).

Examples of compounds of Formula I suitable for use in component (a) ofthe compositions of this invention include the following compounds ofTables 1-5. The following abbreviations are used in the Tables whichfollow: Et is ethyl, Ph is phenyl and CN is cyano. The substituents M, Qand R are equivalent to independent R⁵ substituents that have beenlocated in the positions indicated. The substituents T, U and V areequivalent to independent R⁶ substituents that have been located in thepositions indicated. TABLE 1 Q R M T and V are both Cl and U is H Cl ClH Cl Br H Cl OCF₃ H Cl OCHF₂ H Cl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂H HCl OCFHCF₃ H Cl SCF₃ H Cl SCHF₂ H Cl SCH₂CF₃ H Cl SCF₂CF₃ H Cl SCF₂CF₂HH Cl SCHFCF₃ H Cl SOCF₃ H Cl SOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃ H ClSOCF₂CF₂H H Cl SOCHFCF₃ H Cl SO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ H ClSO₂CF₂CF₃ H Cl SO₂CF₂CF₂H H Cl SO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me BrSO₂CF₃ Me Br SO₂CHF₂ Me Br SO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H MeBr SO₂CHFCF₃ Me Br CN Me Br SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H BrOCF₃ H Br OCHF₂ H Br OCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ HBr SCF₃ H Br SCHF₂ H Br SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃H Br SOCF₃ H Br SOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H BrSOCHFCF₃ H Br SO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H BrSO₂CF₂CF₂H H Br SO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃Me Br SOCF₂CF₃ Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me BrSCF₂CF₂H Me Br SCHFCF₃ Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me ClOCHF₂ Me Cl OCH₂CF₃ Me Cl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me ClSCF₃ Me Cl SCHF₂ Me Cl SCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me ClSCHFCF₃ Me Cl SOCF₃ Me Cl SOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me ClSOCF₂CF₂H Me Cl SOCHFCF₃ Me Cl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ MeCl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂H Me Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br BrMe Br OCF₃ Me Br OCHF₂ Me Br OCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me BrOCHFCF₃ Me Br SCHF₂ Me I I H I I Me T and V are both Cl and U is CH₃ ClCl H Cl Br H Cl OCF₃ H Cl OCHF₂ H Cl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂HH Cl OCHFCF₃ H Cl SCF₃ H Cl SCHF₂ H Cl SCH₂CF₃ H Cl SCF₂CF₃ H ClSCF₂CF₂H H Cl SCHFCF₃ H Cl SOCF₃ H Cl SOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃H Cl SOCF₂CF₂H H Cl SOCHFCF₃ H Cl SO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ HCl SO₂CF₂CF₃ H Cl SO₂CF₂CF₂H H Cl SO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me BrSO₂CF₃ Me Br SO₂CHF₂ Me Br SO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H MeBr SO₂CHFCF₃ Me Br CN Me Br SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H BrOCF₃ H Br OCHF₂ H Br OCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ HBr SCF₃ H Br SCHF₂ H Br SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃H Br SOCF₃ H Br SOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H BrSOCHFCF₃ H Br SO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H BrSO₂CF₂CF₂H H Br SO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃Me Br SOCF₂CF₃ Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me BrSCF₂CF₂H Me Br SCHFCF₃ Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me ClOCHF₂ Me Cl OCH₂CF₃ Me Cl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me ClSCF₃ Me Cl SCHF₂ Me Cl SCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me ClSCHFCF₃ Me Cl SOCF₃ Me Cl SOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me ClSOCF₂CF₂H Me Cl SOCHFCF₃ Me Cl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ MeCl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂H Me Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br BrMe Br OCF₃ Me Br OCHF₂ Me Br OCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me BrOCHFCF₃ Me Br SCHF₂ Me I I H I I Me T is Cl and V and U are both Me ClCl H Cl Br H Cl OCF₃ H Cl OCHF₂ H Cl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂HH Cl OCHFCF₃ H Cl SCF₃ H Cl SCHF₂ H Cl SCH₂CF₃ H Cl SCF₂CF₃ H ClSCF₂CF₂H H Cl SCHFCF₃ H Cl SOCF₃ H Cl SOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃H Cl SOCF₂CF₂H H Cl SOCHFCF₃ H Cl SO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ HCl SO₂CF₂CF₃ H Cl SO₂CF₂CF₂H H Cl SO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me BrSO₂CF₃ Me Br SO₂CHF₂ Me Br SO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H MeBr SO₂CHFCF₃ Me Br CN Me Br SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H BrOCF₃ H Br OCHF₂ H Br OCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ HBr SCF₃ H Br SCHF₂ H Br SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃H Br SOCF₃ H Br SOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H BrSOCHFCF₃ H Br SO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H BrSO₂CF₂CF₂H H Br SO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃Me Br SOCF₂CF₃ Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me BrSCF₂CF₂H Me Br SCHFCF₃ Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me ClOCHF₂ Me Cl OCH₂CF₃ Me Cl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me ClSCF₃ Me Cl SCHF₂ Me Cl SCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me ClSCHFCF₃ Me Cl SOCF₃ Me Cl SOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me ClSOCF₂CF₂H Me Cl SOCHFCF₃ Me Cl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ MeCl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂H Me Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br BrMe Br OCF₃ Me Br OCHF₂ Me Br OCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me BrOCHFCF₃ Me Br SCHF₂ Me I I H I I Me T is Cl, V is I and U is H Cl Cl HCl Br H Cl OCF₃ H Cl OCHF₂ H Cl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂H H ClOCHFCF₃ H Cl SCF₃ H Cl SCHF₂ H Cl SCH₂CF₃ H Cl SCF₂CF₃ H Cl SCF₂CF₂H HCl SCHFCF₃ H Cl SOCF₃ H Cl SOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃ H ClSOCF₂CF₂H H Cl SOCHFCF₃ H Cl SO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ H ClSO₂CF₂CF₃ H Cl SO₂CF₂CF₂H H Cl SO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me BrSO₂CF₃ Me Br SO₂CHF₂ Me Br SO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H MeBr SO₂CHFCF₃ Me Br CN Me Br SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H BrOCF₃ H Br OCHF₂ H Br OCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ HBr SCF₃ H Br SCHF₂ H Br SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃H Br SOCF₃ H Br SOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H BrSOCHFCF₃ H Br SO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H BrSO₂CF₂CF₂H H Br SO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃Me Br SOCF₂CF₃ Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me BrSCF₂CF₂H Me Br SCHFCF₃ Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me ClOCHF₂ Me Cl OCH₂CF₃ Me Cl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me ClSCF₃ Me Cl SCHF₂ Me Cl SCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me ClSCHFCF₃ Me Cl SOCF₃ Me Cl SOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me ClSOCF₂CF₂H Me Cl SOCHFCF₃ Me Cl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ MeCl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂H Me Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br BrMe Br OCF₃ Me Br OCHF₂ Me Br OCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me BrOCHFCF₃ Me Br SCHF₂ Me I I H I I Me T is Cl, V is I and U is Me Cl Cl HCl Br H Cl OCF₃ H Cl OCHF₂ H Cl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂H H ClOCHFCF₃ H Cl SCF₃ H Cl SCHF₂ H Cl SCH₂CF₃ H Cl SCF₂CF₃ H Cl SCF₂CF₂H HCl SCHFCF₃ H Cl SOCF₃ H Cl SOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃ H ClSOCF₂CF₂H H Cl SOCHFCF₃ H Cl SO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ H ClSO₂CF₂CF₃ H Cl SO₂CF₂CF₂H H Cl SO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me BrSO₂CF₃ Me Br SO₂CHF₂ Me Br SO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H MeBr SO₂CHCFCF₃ Me Br CN Me Br SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H BrOCF₃ H Br OCHF₂ H Br OCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ HBr SCF₃ H Br SCHF₂ H Br SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃H Br SOCF₃ H Br SOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H BrSOCHFCF₃ H Br SO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H BrSO₂CF₂CF₂H H Br SO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃Me Br SOCF₂CF₃ Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me BrSCF₂CF₂H Me Br SCHFCF₃ Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me ClOCHF₂ Me Cl OCH₂CF₃ Me Cl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me ClSCF₃ Me Cl SCHF₂ Me Cl SCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me ClSCHFCF₃ Me Cl SOCF₃ Me Cl SOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me ClSOCF₂CF₂H Me Cl SOCHFCF₃ Me Cl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ MeCl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂H Me Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br BrMe Br OCF₃ Me Br OCHF₂ Me Br OCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me BrOCHFCF₃ Me Br SCHF₂ Me I I H I I Me T is F, V is I and U is H Cl Cl H ClBr H Cl OCF₃ H Cl OCHF₂ H Cl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂H H ClOCHFCF₃ H Cl SCF₃ H Cl SCHF₂ H Cl SCH₂CF₃ H Cl SCF₂CF₃ H Cl SCF₂CF₂H HCl SCHFCF₃ H Cl SOCF₃ H Cl SOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃ H ClSOCF₂CF₂H H Cl SOCHFCF₃ H Cl SO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ H ClSO₂CF₂CF₃ H Cl SO₂CF₂CF₂H H Cl SO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me BrSO₂CF₃ Me Br SO₂CHF₂ Me Br SO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H MeBr SO₂CHFCF₃ Me Br CN Me Br SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H BrOCF₃ H Br OCHF₂ H Br OCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ HBr SCF₃ H Br SCHF₂ H Br SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃H Br SOCF₃ H Br SOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H BrSOCHFCF₃ H Br SO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H BrSO₂CF₂CF₂H H Br SO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃Me Br SOCF₂CF₃ Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me BrSCF₂CF₂H Me Br SCHFCF₃ Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me ClOCHF₂ Me Cl OCH₂CF₃ Me Cl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me ClSCF₃ Me Cl SCHF₂ Me Cl SCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me ClSCHFCF₃ Me Cl SOCF₃ Me Cl SOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me ClSOCF₂CF₂H Me Cl SOCHFCF₃ Me Cl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ MeCl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂H Me Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br BrMe Br OCF₃ Me Br OCHF₂ Me Br OCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me BrOCHFCF₃ Me Br SCHF₂ Me I I H I I Me T is I, V is Cl and U is H Cl Cl HCl Br H Cl OCF₃ H Cl OCHF₂ H Cl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂H H ClOCHFCF₃ H Cl SCF₃ H Cl SCHF₂ H Cl SCH₂CF₃ H Cl SCF₂CF₃ H Cl SCF₂CF₂H HCl SCHFCF₃ H Cl SOCF₃ H Cl SOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃ H ClSOCF₂CF₂H H Cl SOCHFCF₃ H Cl SO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ H ClSO₂CF₂CF₃ H Cl SO₂CF₂CF₂H H Cl SO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me BrSO₂CF₃ Me Br SO₂CHF₂ Me Br SO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H MeBr SO₂CHFCF₃ Me Br CN Me Br SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H BrOCF₃ H Br OCHF₂ H Br OCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ HBr SCF₃ H Br SCHF₂ H Br SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃H Br SOCF₃ H Br SOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H BrSOCHFCF₃ H Br SO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H BrSO₂CF₂CF₂H H Br SO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃Me Br SOCF₂CF₃ Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me BrSCF₂CF₂H Me Br SCHFCF₃ Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me ClOCHF₂ Me Cl OCH₂CF₃ Me Cl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me ClSCF₃ Me Cl SCHF₂ Me Cl SCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me ClSCHFCF₃ Me Cl SOCF₃ Me Cl SOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me ClSOCF₂CF₂H Me Cl SOCHFCF₃ Me Cl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ MeCl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂H Me Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br BrMe Br OCF₃ Me Br OCHF₂ Me Br OCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me BrOCHFCF₃ Me Br SCHF₂ Me I I H I I Me

TABLE 2

Q R M T and V are both Cl and U is H Cl Cl H Cl Br H Cl OCF₃ H Cl OCHF₂H Cl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂H H Cl OCHFCF₃ H Cl SCF₃ H ClSCHF₂ H Cl SCH₂CF₃ H Cl SCF₂CF₃ H Cl SCF₂CF₂H H Cl SCHFCF₃ H Cl SOCF₃ HCl SOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃ H Cl SOCF₂CF₂H H Cl SOCHFCF₃ H ClSO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ H Cl SO₂CF₂CF₃ H Cl SO₂CF₂CF₂H H ClSO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me Br SO₂CF₃ Me Br SO₂CHF₂ Me BrSO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H Me Br SO₂CHFCF₃ Me Br CN MeBr SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H Br OCF₃ H Br OCHF₂ H BrOCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ H Br SCF₃ H Br SCHF₂ HBr SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃ H Br SOCF₃ H BrSOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H Br SOCHFCF₃ H BrSO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H Br SO₂CF₂CF₂H H BrSO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃ Me Br SOCF₂CF₃Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me Br SCF₂CF₂H Me Br SCHFCF₃Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me Cl OCHF₂ Me Cl OCH₂CF₃ MeCl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me Cl SCF₃ Me Cl SCHF₂ Me ClSCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me Cl SCHFCF₃ Me Cl SOCF₃ Me ClSOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me Cl SOCF₂CF₂H Me Cl SOCHFCF₃ MeCl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ Me Cl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂HMe Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br Br Me Br OCF₃ Me Br OCHF₂ Me BrOCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me Br OCHFCF₃ Me Br SCHF₂ Me I I HI I Me T and V are both Cl and U is CH₃ Cl Cl H Cl Br H Cl OCF₃ H ClOCHF₂ H Cl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂H H Cl OCHFCF₃ H Cl SCF₃ HCl SCHF₂ H Cl SCH₂CF₃ H Cl SCF₂CF₃ H Cl SCF₂CF₂H H Cl SCHFCF₃ H Cl SOCF₃H Cl SOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃ H Cl SOCF₂CF₂H H Cl SOCHFCF₃ HCl SO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ H Cl SO₂CF₂CF₃ H Cl SO₂CF₂CF₂H HCl SO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me Br SO₂CF₃ Me Br SO₂CHF₂ Me BrSO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H Me Br SO₂CHFCF₃ Me Br CN MeBr SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H Br OCF₃ H Br OCHF₂ H BrOCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ H Br SCF₃ H Br SCHF₂ HBr SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃ H Br SOCF₃ H BrSOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H Br SOCHFCF₃ H BrSO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H Br SO₂CF₂CF₂H H BrSO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃ Me Br SOCF₂CF₃Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me Br SCF₂CF₂H Me Br SCHFCF₃Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me Cl OCHF₂ Me Cl OCH₂CF₃ MeCl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me Cl SCF₃ Me Cl SCHF₂ Me ClSCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me Cl SCHFCF₃ Me Cl SOCF₃ Me ClSOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me Cl SOCF₂CF₂H Me Cl SOCHFCF₃ MeCl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ Me Cl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂HMe Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br Br Me Br OCF₃ Me Br OCHF₂ Me BrOCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me Br OCHFCF₃ Me Br SCHF₂ Me I I HI I Me T is Cl and V and U are both Me Cl Cl H Cl Br H Cl OCF₃ H ClOCHF₂ H Cl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂H H Cl OCHFCF₃ H Cl SCF₃ HCl SCHF₂ H Cl SCH₂CF₃ H Cl SCF₂CF₃ H Cl SCF₂CF₂H H Cl SCHFCF₃ H Cl SOCF₃H Cl SOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃ H Cl SOCF₂CF₂H H Cl SOCHFCF₃ HCl SO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ H Cl SO₂CF₂CF₃ H Cl SO₂CF₂CF₂H HCl SO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me Br SO₂CF₃ Me Br SO₂CHF₂ Me BrSO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H Me Br SO₂CHFCF₃ Me Br CN MeBr SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H Br OCF₃ H Br OCHF₂ H BrOCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ H Br SCF₃ H Br SCHF₂ HBr SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃ H Br SOCF₃ H BrSOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H Br SOCHFCF₃ H BrSO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H Br SO₂CF₂CF₂H H BrSO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃ Me Br SOCF₂CF₃Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me Br SCF₂CF₂H Me Br SCHFCF₃Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me Cl OCHF₂ Me Cl OCH₂CF₃ MeCl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me Cl SCF₃ Me Cl SCHF₂ Me ClSCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me Cl SCHFCF₃ Me Cl SOCF₃ Me ClSOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me Cl SOCF₂CF₂H Me Cl SOCHFCF₃ MeCl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ Me Cl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂HMe Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br Br Me Br OCF₃ Me Br OCHF₂ Me BrOCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me Br OCHFCF₃ Me Br SCHF₂ Me I I HI I Me T is Cl, V is I and U is H Cl Cl H Cl Br H Cl OCF₃ H Cl OCHF₂ HCl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂H H Cl OCHFCF₃ H Cl SCF₃ H Cl SCHF₂H Cl SCH₂CF₃ H Cl SCF₂CF₃ H Cl SCF₂CF₂H H Cl SCHFCF₃ H Cl SOCF₃ H ClSOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃ H Cl SOCF₂CF₂H H Cl SOCHFCF₃ H ClSO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ H Cl SO₂CF₂CF₃ H Cl SO₂CF₂CF₂H H ClSO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me Br SO₂CF₃ Me Br SO₂CHF₂ Me BrSO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H Me Br SO₂CHFCF₃ Me Br CN MeBr SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H Br OCF₃ H Br OCHF₂ H BrOCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ H Br SCF₃ H Br SCHF₂ HBr SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃ H Br SOCF₃ H BrSOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H Br SOCHFCF₃ H BrSO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H Br SO₂CF₂CF₂H H BrSO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃ Me Br SOCF₂CF₃Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me Br SCF₂CF₂H Me Br SCHFCF₃Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me Cl OCHF₂ Me Cl OCH₂CF₃ MeCl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me Cl SCF₃ Me Cl SCHF₂ Me ClSCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me Cl SCHFCF₃ Me Cl SOCF₃ Me ClSOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me Cl SOCF₂CF₂H Me Cl SOCHFCF₃ MeCl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ Me Cl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂HMe Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br Br Me Br OCF₃ Me Br OCHF₂ Me BrOCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me Br OCHFCF₃ Me Br SCHF₂ Me I I HI I Me T is Cl, V is I and U is Me Cl Cl H Cl Br H Cl OCF₃ H Cl OCHF₂ HCl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂H H Cl OCHFCF₃ H Cl SCF₃ H Cl SCHF₂H Cl SCH₂CF₃ H Cl SCF₂CF₃ H Cl SCF₂CF₂H H Cl SCHFCF₃ H Cl SOCF₃ H ClSOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃ H Cl SOCF₂CF₂H H Cl SOCHFCF₃ H ClSO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ H Cl SO₂CF₂CF₃ H Cl SO₂CF₂CF₂H H ClSO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me Br SO₂CF₃ Me Br SO₂CHF₂ Me BrSO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H Me Br SO₂CHFCF₃ Me Br CN MeBr SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H Br OCF₃ H Br OCHF₂ H BrOCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ H Br SCF₃ H Br SCHF₂ HBr SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃ H Br SOCF₃ H BrSOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H Br SOCHFCF₃ H BrSO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H Br SO₂CF₂CF₂H H BrSO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃ Me Br SOCF₂CF₃Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me Br SCF₂CF₂H Me Br SCHFCF₃Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me Cl OCHF₂ Me Cl OCH₂CF₃ MeCl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me Cl SCF₃ Me Cl SCHF₂ Me ClSCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me Cl SCHFCF₃ Me Cl SOCF₃ Me ClSOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me Cl SOCF₂CF₂H Me Cl SOCHFCF₃ MeCl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ Me Cl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂HMe Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br Br Me Br OCF₃ Me Br OCHF₂ Me BrOCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me Br OCHFCF₃ Me Br SCHF₂ Me I I HI I Me T is F, V is I and U is H Cl Cl H Cl Br H Cl OCF₃ H Cl OCHF₂ H ClOCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂H H Cl OCHFCF₃ H Cl SCF₃ H Cl SCHF₂ HCl SCH₂CF₃ H Cl SCF₂CF₃ H Cl SCF₂CF₂H H Cl SCHFCF₃ H Cl SOCF₃ H ClSOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃ H Cl SOCF₂CF₂H H Cl SOCHFCF₃ H ClSO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ H Cl SO₂CF₂CF₃ H Cl SO₂CF₂CF₂H H ClSO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me Br SO₂CF₃ Me Br SO₂CHF₂ Me BrSO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H Me Br SO₂CHFCF₃ Me Br CN MeBr SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H Br OCF₃ H Br OCHF₂ H BrOCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ H Br SCF₃ H Br SCHF₂ HBr SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃ H Br SOCF₃ H BrSOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H Br SOCHFCF₃ H BrSO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H Br SO₂CF₂CF₂H H BrSO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃ Me Br SOCF₂CF₃Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me Br SCF₂CF₂H Me Br SCHFCF₃Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me Cl OCHF₂ Me Cl OCH₂CF₃ MeCl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me Cl SCF₃ Me Cl SCHF₂ Me ClSCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me Cl SCHFCF₃ Me Cl SOCF₃ Me ClSOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me Cl SOCF₂CF₂H Me Cl SOCHFCF₃ MeCl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ Me Cl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂HMe Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br Br Me Br OCF₃ Me Br OCHF₂ Me BrOCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me Br OCHFCF₃ Me Br SCHF₂ Me I I HI I Me T is I, V is Cl and U is H Cl Cl H Cl Br H Cl OCF₃ H Cl OCHF₂ HCl OCH₂CF₃ H Cl OCF₂CF₃ H Cl OCF₂CF₂H H Cl OCHFCF₃ H Cl SCF₃ H Cl SCHF₂H Cl SCH₂CF₃ H Cl SCF₂CF₃ H Cl SCF₂CF₂H H Cl SCHFCF₃ H Cl SOCF₃ H ClSOCHF₂ H Cl SOCH₂CF₃ H Cl SOCF₂CF₃ H Cl SOCF₂CF₂H H Cl SOCHFCF₃ H ClSO₂CF₃ H Cl SO₂CHF₂ H Cl SO₂CH₂CF₃ H Cl SO₂CF₂CF₃ H Cl SO₂CF₂CF₂H H ClSO₂CHFCF₃ H Cl CN H Br SOCHFCF₃ Me Br SO₂CF₃ Me Br SO₂CHF₂ Me BrSO₂CH₂CF₃ Me Br SO₂CF₂CF₃ Me Br SO₂CF₂CF₂H Me Br SO₂CHFCF₃ Me Br CN MeBr SCF₃ Me Cl I H Cl I Me Br Cl H Br Br H Br OCF₃ H Br OCHF₂ H BrOCH₂CF₃ H Br OCF₂CF₃ H Br OCF₂CF₂H H Br OCHFCF₃ H Br SCF₃ H Br SCHF₂ HBr SCH₂CF₃ H Br SCF₂CF₃ H Br SCF₂CF₂H H Br SCHFCF₃ H Br SOCF₃ H BrSOCHF₂ H Br SOCH₂CF₃ H Br SOCF₂CF₃ H Br SOCF₂CF₂H H Br SOCHFCF₃ H BrSO₂CF₃ H Br SO₂CHF₂ H Br SO₂CH₂CF₃ H Br SO₂CF₂CF₃ H Br SO₂CF₂CF₂H H BrSO₂CHFCF₃ H Br CN H Br SOCF₃ Me Br SOCHF₂ Me Br SOCH₂CF₃ Me Br SOCF₂CF₃Me Br SOCF₂CF₂H Me Br SCH₂CF₃ Me Br SCF₂CF₃ Me Br SCF₂CF₂H Me Br SCHFCF₃Me Br I H Br I Me Cl Cl Me Cl Br Me Cl OCF₃ Me Cl OCHF₂ Me Cl OCH₂CF₃ MeCl OCF₂CF₃ Me Cl OCF₂CF₂H Me Cl OCHFCF₃ Me Cl SCF₃ Me Cl SCHF₂ Me ClSCH₂CF₃ Me Cl SCF₂CF₃ Me Cl SCF₂CF₂H Me Cl SCHFCF₃ Me Cl SOCF₃ Me ClSOCHF₂ Me Cl SOCH₂CF₃ Me Cl SOCF₂CF₃ Me Cl SOCF₂CF₂H Me Cl SOCHFCF₃ MeCl SO₂CF₃ Me Cl SO₂CHF₂ Me Cl SO₂CH₂CF₃ Me Cl SO₂CF₂CF₃ Me Cl SO₂CF₂CF₂HMe Cl SO₂CHFCF₃ Me Cl CN Me Br Cl Me Br Br Me Br OCF₃ Me Br OCHF₂ Me BrOCH₂CF₃ Me Br OCF₂CF₃ Me Br OCF₂CF₂H Me Br OCHFCF₃ Me Br SCHF₂ Me I I HI I Me

TABLE 3

Q R² U I H H OCHF₂ H H OCH₂F H H OCF₂Cl H H OCH₂CF₃ H H Et H H CN H HSCF₃ H H SCHF₂ H H SCH₂F H H Ph H H SiMe₃ H H I Me Me OCHF₂ Me Me OCH₂FMe Me OCF₂Cl Me Me I Me H OCHF₂ Me H OCH₂F Me H OCF₂Cl Me H OCH₂CF₃ Me HEt Me H CN Me H SCF₃ Me H SCHF₂ Me H SCH₂F Me H Ph Me H SiMe₃ Me H CN MeMe SCF₃ Me Me OCH₂CF₃ Me Me Et Me Me I H Me OCHF₂ H Me OCH₂F H Me OCF₂ClH Me OCH₂CF₃ H Me Et H Me CN H Me SCF₃ H Me SCHF₂ H Me SCH₂F H Me Ph HMe SiMe₃ H Me SCHF₂ Me Me SCH₂F Me Me Ph Me Me SiMe₃ Me Me

TABLE 4

Q R² U I H H OCHF₂ H H OCH₂F H H OCF₂Cl H H OCH₂CF₃ H H Et H H CN H HSCF₃ H H SCHF₂ H H SCH₂F H H Ph H H SiMe₃ H H I Me Me OCHF₂ Me Me OCH₂FMe Me OCF₂Cl Me Me I Me H OCHF₂ Me H OCH₂F Me H OCF₂Cl Me H OCH₂CF₃ Me HEt Me H CN Me H SCF₃ Me H SCHF₂ Me H SCH₂F Me H Ph Me H SiMe₃ Me H CN MeMe SCF₃ Me Me OCH₂CF₃ Me Me Et Me Me I H Me OCHF₂ H Me OCH₂F H Me OCF₂ClH Me OCH₂CF₃ H Me Et H Me CN H Me SCF₃ H Me SCHF₂ H Me SCH₂F H Me Ph HMe SiMe₃ H Me SCHF₂ Me Me SCH₂F Me Me Ph Me Me SiMe₃ Me Me

TABLE 5

Q R² U I H H OCHF₂ H H OCH₂F H H OCF₂Cl H H OCH₂CF₃ H H Et H H CN H HSCF₃ H H SCHF₂ H H SCH₂F H H Ph H H SiMe₃ H H I Me Me OCHF₂ Me Me OCH₂FMe Me OCF₂Cl Me Me I Me H OCHF₂ Me H OCH₂F Me H OCF₂Cl Me H OCH₂CF₃ Me HEt Me H CN Me H SCF₃ Me H SCHF₂ Me H SCH₂F Me H Ph Me H SiMe₃ Me H CN MeMe SCF₃ Me Me OCH₂CF₃ Me Me Et Me Me I H Me OCHF₂ H Me OCH₂F H Me OCF₂ClH Me OCH₂CF₃ H Me Et H Me CN H Me SCF₃ H Me SCHF₂ H Me SCH₂F H Me Ph HMe SiMe₃ H Me SCHF₂ Me Me SCH₂F Me Me Ph Me Me SiMe₃ Me Me

The fungicides of component (b) of the compositions of the invention areselected from the group consisting of

-   -   (b1) alkylenebis(dithiocarbamate) fungicides;    -   (b2) compounds acting at the bc, complex of the fungal        mitochondrial respiratory electron transfer site;    -   (b3) cymoxanil;    -   (b4) compounds acting at the demethylase enzyme of the sterol        biosynthesis pathway;    -   (b5) morpholine and piperidine compounds that act on the sterol        biosynthesis pathway;    -   (b6) phenylamide fungicides;    -   (b7) pyrimidinone fungicides;    -   (b8) phthalimides; and    -   (b9) fosetyl-aluminum.

The weight ratios of component (b) to component (a) typically is from100:1 to 1:100, preferably is from 30:1 to 1:30, and more preferably isfrom 10:1 to 1:10. Of note are compositions wherein the weight ratio ofcomponent (b) to component (a) is from 10:1 to 1:1. Included arecompositions wherein the weight ratio of component (b) to component (a)is from 9:1 to 4.5:1.

The bc₁ Complex Fungicides (Component (b2))

Strobilurin fungicides such as azoxystrobin, kresoxim-methyl,metominostrobin/fenominostrobin (SSF-126), picoxystrobin, pyraclostrobinand trifloxystrobin are known to have a fungicidal mode of action whichinhibits the bc₁ complex in the mitochondrial respiration chain (Angew.Chem. Int. Ed., 1999, 38, 1328-1349). Methyl(E)-2-[[6-(2-cyanophenoxy)-4-pyrimidinyl]oxy]-α-(methoxyimino)benzeneacetate(also known as azoxystrobin) is described as a bc, complex inhibitor inBiochemical Society Transactions 1993, 22, 68S. Methyl(E)-α-(methoxyimino)-2-[(2-methylphenoxy)methyl]benzeneacetate (alsoknown as kresoxim-methyl) is described as a bc₁ complex inhibitor inBiochemical Society Transactions 1993, 22, 64S.(E)-2-[(2,5-Dimethylphenoxy)methyl]-α-(methoxyimino)-N-methylbenzeneacetamideis described as a bc₁ complex inhibitor in Biochemistry and Cell Biology1995, 85(3), 306-311. Other compounds that inhibit the bc₁ complex inthe mitochondrial respiration chain include famoxadone and fenamidone.

The bc₁ complex is sometimes referred to by other names in thebiochemical literature, including complex III of the electron transferchain, and ubihydroquinone:cytochrome c oxidoreductase. It is uniquelyidentified by the Enzyme Commission number EC1.10.2.2. The bc₁ complexis described in, for example, J. Biol. Chem. 1989, 264, 14543-38;Methods Enzymol. 1986, 126. 253-71; and references cited therein.

The Sterol Biosynthesis Inhibitor Fungicides (component (b4) or (b5))The class of sterol biosynthesis inhibitors includes DMI and non-DMIcompounds, that control fungi by inhibiting enzymes in the sterolbiosynthesis pathway. DMI fungicides have a common site of action withinthe fungal sterol biosynthesis pathway; that is, an inhibition ofdemethylation at position 14 of lanosterol or 24-methylenedihydrolanosterol, which are precursors to sterols in fungi. Compoundsacting at this site are often referred to as demethylase inhibitors, DMIfungicides, or DMIs. The demethylase enzyme is sometimes referred to byother names in the biochemical literature, including cytochrome P-450(14DM). The demethylase enzyme is described in, for example, J. Biol.Cheem. 1992, 267, 13175-79 and references cited therein. DMI fungicidesfall into several classes: azoles (including triazoles and imidazoles),pyrimidines, piperazines and pyridines. The triazoles includesbromuconazole, cyproconazole, difenoconazole, diniconazole,epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol,hexaconazole, ipconazole, metconazole, penconazole, propiconazole,tebuconazole, tetraconazole, triadimefon, triadirnenol, triticonazoleand uniconazole. The imidazoles include clotrimazole, econazole,imazalil, isoconazole, miconazole and pro chloraz. The pyrimidinesinclude fenarimol, nuarimol and triarimol. The piperazines includetriforine. The pyridines include buthiobate and pyrifenox. Biochemicalinvestigations have shown that all of the above mentioned fungicides areDMI fungicides as described by K. H. Kuck, et al. in Modern SelectiveFungicides—Properties, Applications and Mechanisms of Action, Lyr, H.,Ed.; Gustav Fischer Verlag: New York, 1995, 205-258.

The DMI fungicides have been grouped together to distinguish them fromother sterol biosytithesis inhibitors, such as, the morpholine andpiperidine fungicides. The morpholines and piperidines are also sterolbiosynthesis inhibitors but have been shown to inhibit later steps inthe sterol biosynthesis pathway. The morpholines include aldimorph,dodemorph, fenpropiniorph, tridemorph and trimorphamide. The piperidinesinclude fenpropidin. Biochemical investigations have shown that all ofthe above mentioned morpholine and piperidine fungicides are sterolbiosynthesis inhibitor fungicides as described by K. H. Kuck, et al. inModern Selective Fungicides—Properties, Applications and Mechanisms ofAction, Lyr, H., Ed.; Gustav Fischer Verlag: New York, 1995, 185-204.

Pyrimidinone Fungicides (Component (b7))

Pyrimidinone fungicides include compounds of Formula II

wherein

-   -   G is a fused phenyl, thiophene or pyridine ring;    -   R¹ is C₁-C₆ alkyl;    -   R² is C₁-C₆ alkyl or C₁-C₆ alkoxy;    -   R³ is halogen; and    -   R⁴ is hydrogen or halogen.

Pyrimidinone fungicides are described in International PatentApplication WO94/26722, U.S. Pat. No. 6,066,638, U.S. Pat. No.6,245,770, U.S. Pat. No. 6,262,058 and U.S. Pat. No. 6,277,858.

Of note are pyrimidinone fungicides selected from the group:

-   6-bromo-3-propyl-2-propyloxy-4(3 Hr)-quinazolinone,-   6,8-diiodo-3-propyl-2-propyloxy-4(3H)-quinazolinone,-   6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone,-   6-chloro-2-propoxy-3-propylthieno[2,3-<d]pyrimidin-4(3H)-one,-   6-bromo-2-propoxy-3-propylthieno[2,3-d]pyrimidin-4(3H)-one,-   7-bromo-2-propoxy-3-propylthieno[3,2-d]pyrimidin-4(3H)-one,-   6-bromo-2-propoxy-3-propylpyrido[2,3-d]pyrimidin-4(3H)-one,-   6,7-dibromo-2-propoxy-3-propylthieno[3,2-d]pyrimidin-4(3H)-one, and

3-(cyclopropylmethyl)-6-iodo-2-(propylthio)pyrido[2,3-d]pyrimidin-4(3H)-one.TABLE 7 Examples of component (b) (b1) Alkylenebis(dithiocarbamate)ssuch as mancozeb, maneb, propineb and zineb (b3) Cymoxanil (b6)Phenylamides such as metalaxyl, benalaxyl and oxadixyl (b8) Phthalimidssuch as folpet or captan (b9) Fosetyl-aluminum

Other fungicides which can be included in compositions of this inventionin combination with a Formula I compound or as an additional componentin combination with component (a) and component (b) are acibenzolar,benalaxyl, benomyl, blasticidin-S, Bordeaux mixture (tribasic coppersulfate), carpropamid, captafol, captan, carbendazim, chloroneb,chlorothalonil, copper oxychloride, copper salts such as copper sulfateand copper hydroxide, cyazofamid, cymoxanil, cyprodinil,(S)-3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide(RH 7281), diclocymet (S-2900), diclomezme, dicloran, dimethomorph,diniconazole-M, dodemorph, dodine, edifenphos, fencaramid (SZX0722),fenpiclonil, fentin acetate, fentin hydroxide, fluazinam, fludioxonil,flumetover (RPA 403397), flutolanil, folpet, fosetyl-alurtninum,furalaxyl, furametapyr (S-82658), iprobenfos, iprodione, isoprothiolane,iprovalicarb, kasugamycin, mancozeb, maneb, mefenoxam, mepronil,metalaxyl, metiram-zinc, myclobutanil, neo-asozin (ferricmethanearsonate), oxadixyl, pencycuron, prochloraz, procymidone,propamocarb, propineb, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen,spiroxamine, sulfur, thifluzamide, thiophanate-methyl, thiram,triadimefon, tricyclazole, validamycin, vinclozolin, zineb and zoxamid.

Descriptions of the commercially available compounds listed above may befound in The Pesticide Manual, Twelfth Edition, C. D. S. Tomlin, ed.,British Crop Protection Council, 2000.

Of note are combinations of Formula I with fungicides of a differentbiochemical mode of action (e.g. mitochondrial respiration inhibition,inhibition of protein synthesis by interference of the synthesis ofribosomal RNA or inhibition of beta-tubulin synthesis) that can beparticularly advantageous for resistance management. Examples includecombinations of compounds of Formula I (e.g. Compound 1) withstrobilurins such as azoxystrobin, kresoxim-methyl, pyraclostrobin andtrifloxystrobin; carbendazim, mitochondrial respiration inhibitors suchas famoxadone and fenamidone; benomyl, cymoxanil; dimethomorph; folpet;fosetyl-aluminum; metalaxyl; mancozeb and maneb. These combinations canbe particularly advantageous for resistance management, especially wherethe fungicides of the combination control the same or similar diseases.

Of note are combinations of Formula I with fungicides for controllinggrape diseases (e.g. Plasmopara viticola, Bottytis cinerea and Uncinulanecatur) including alkylenebis(dithiocarbamate)s such as mancozeb,maneb, propineb and zineb, phthalimids such as folpet, copper salts suchas copper sulfate and copper hydroxide, strobilurins such asazoxystrobin, pyraclostrobin and trifloxystrobin, mitochondrialrespiration inhibitors such as famoxadone and fenamidone, phenylamidessuch as metalaxyl, phosphonates such as fosetyl-A1, dimethomorph,pyrimidinone fungicides such as6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone and6-chloro-2-propoxy-3-propylthieno[2,3-d]pyrimidin-4(3H)-one, and otherfungicides such as cymoxanil.

Of note are combinations of Formula I with fungicides for controllingpotato diseases (e.g. Phytophthora infestans, Alternaria solani andRhizoctonia solani) including alkylenebis(dithiocarbamate)s such asmancozeb, maneb, propineb and zineb; copper salts such as copper sulfateand copper hydroxide; strobilurins such as pyraclostrobin andtrifloxystrobin; mitochondrial respiration inhibitors such as famoxadoneand fenamidone; phenylamides such as metalaxyl; carbamates such aspropamocarb; phenylpyridylamines such as fluazinam and other fungicidessuch as chlorothalonil, cyazofamid, cymoxanil, dimethomorph, zoxamid andiprovalicarb.

Of note are compositions wherein component (b) comprises at least onecompound from each of two different groups selected from (b1), (b2),(b3), (b4), (b5), (b6), (b7), (b8) and (b9). The weight ratio of thecompound(s) of the first of these two component (b) groups to thecompound(s) of the second of these component (b) groups typically isfrom 100:1 to 1:100, more typically from 30:1 to 1:30 and most typicallyfrom 10:1 to 1:10.

Of note are compositions wherein component (b) comprises at least onecompound selected from (b1), for example mancozeb, and at least onecompound selected from a second component (b) group, for example, from(b2), (b3), (b6), (b7), (b8) or (b9). Of particular note are suchcompositions wherein the overall weight ratio of component (b) tocomponent (a) is from 30:1 to 1:30 and the weight ratio of component(b1) to component (a) is from 10:1 to 1:1. Included are compositionswherein the weight ratio of component (b1) to component (a) is from 9:1to 4.5:1. Examples of these compositions include compositions comprisingmixtures of component (a) (preferably a compound from Index Table A)with mancozeb and a compound selected from the group consisting offamoxadone, fenamidone, azoxysirobin, kresoxim-methyl, pyraclostrobin,trifloxystrobin, cymoxanil, metalaxyl, benalaxyl, oxadixyl,6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone,6-chloro-2-propoxy-3-propylthieno[2,3-d]pyrimidin-4(3H)-one, folpet,captan and fosetyl-aluminum.

Also of note are compositions wherein component (b) comprises at leastone compound selected from (b2), for example famoxadone, and at leastone compound selected from a second component (b) group, for example,from (b1), (b3), (b6), (b7), (b8) or (b9). Of particular note are suchcompositions wherein the overall weight ratio of component (b) tocomponent (a) is from 30:1 to 1:30 and the weight ratio of component(b2) to component (a) is from 10:1 to 1:1. Included are compositionswherein the weight ratio of component (b2) to component (a) is from 9:1to 4.5:1. Examples of these compositions include compositions comprisingmixtures of component (a) (preferably a compound from Index Table A)with fatnoxadone and a compound selected from the group consisting ofmancozeb, maneb, propineb, zineb, cymoxanil, metalaxyl, benalaxyl,oxadixyl, 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone,6-chloro-2-propoxy-3-propylthieno[2,3-d]pyrimidin-4(3H)-one, folpet,captan and fosetyl-aluminum.

Also of note are compositions wherein component (b) comprises thecompound of (b3), in other words cymoxanil, and at least one compoundselected from a second component (b) group, for example, from (b1),(b2), (b6), (b7), (b8) or (b9). Of particular note are such compositionswherein the overall weight ratio of component (b) to component (a) isfrom 30:1 to 1:30 and the weight ratio of component (b3) to component(a) is from 10:1 to 1:1. Included are compositions wherein the weightratio of component (b3) to component (a) is from 9:1 to 4.5:1. Examplesof these compositions include compositions comprising mixtures ofcomponent (a) (preferably a compound from Index Table A) with cymoxaniland a compound selected from the group consisting of famoxadone,fenamidone, azoxystrobin, kresoxim-methyl, pyraclostrobin,trifloxystrobin, mancozeb, maneb, propineb, zineb, metalaxyl, benalaxyl,oxadixyl, 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone,6-chloro-2-propoxy-3-propylthieno[2,3-d]pyrimidin-4(3H)-one, folpet,captan and fosetyl-aluminum.

Also of note are compositions wherein component (b) comprises at leastone compound selected from (b6), for example metalaxyl, and at least onecompound selected from a second component (b) group, for example, from(b1), (b2), (b3), (b7), (b8) or (b9). Of particular note are suchcompositions wherein the overall weight ratio of component (b) tocomponent (a) is from 30:1 to 1:30 and the weight ratio of component(b6) to component (a) is from 10:1 to 1:3. Included are compositionswherein the weight ratio of component (b6) to component (a) is from 9:1to 4.5:1. Examples of these compositions include compositions comprisingmixtures of component (a) (preferably a compound from Index Table A)with metalaxyl or oxadixyl and a compound selected from the groupconsisting of famoxadone, fenamidone, azoxystrobin, kresoxim-methyl,pyraclostrobin, trifloxystrobin, cymoxanil, mancozeb, maneb, propineb,zineb, 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone,6-chloro-2-propoxy-3-propylthieno[2,3-d]pyrimidin-4(3H)-one, folpet,captan and fosetyl-aluminum.

Also of note are compositions wherein component (b) comprises at leastone compound selected from (b7), for example6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone or6-chloro-2-propoxy-3-propylthieno[2,3-d]pyrimidin-4(3H)-one, and atleast one compound selected from a second component (b) group, forexample, from (b1), (b2), (b3), (b6), (b8) or (b9). Of particular noteare such compositions wherein the overall weight ratio of component (b)to component (a) is from 30:1 to 1:30 and the weight ratio of component(b7) to component (a) is from 1:1 to 1:20. Included are compositionswherein the weight ratio of component (b6) to component (a) is from1:4.5 to 1:9. Examples of these compositions include compositionscomprising mixtures of component (a) (preferably a compound from IndexTable A) with 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone or6-chloro-2-propoxy-3-propylthieno[2,3-d]pyrimidin-4(3H)-one and acompound selected from the group consisting of famoxadone, fenamidone,azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin,cymoxanil, mancozeb, maneb, propineb, zineb, metalaxyl, benalaxyl,oxadixyl, folpet, captan and fosetyl-aluminum.

Also of note are compositions wherein component (b) comprises thecompound of (b9, in other words fosetyl-aluminum, and at least onecompound selected from a second component (b) group, for example, from(b1), (b2), (b3), (b6) or (b7). Of particular note are such compositionswherein the overall weight ratio of component (b) to component (a) isfrom 30:1 to 1:30 and the weight ratio of component (b9) to component(a) is from 10:1 to 1:1. Included are compositions wherein the weightratio of component (b9) to component (a) is from 9:1 to 4.5:1. Examplesof these compositions include compositions comprising mixtures ofcomponent (a) (preferably a compound from Index Table A) withfosetyl-aluminum and a compound selected from the group consisting offamoxadone, fenamidone, azoxystrobin, kresoxim-methyl, pyraclostrobin,trifloxystrobin, mancozeb, maneb, propineb, zineb, metalaxyl, benalaxyl,oxadixyl, 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone,6-chloro-2-propoxy-3-propylthieno[2,3-d]pyrimidin-4(3H)-one, folpet,captan and cymoxanil.

Of note are combinations of compounds of Formula I with fungicidesgiving an even broader spectrum of agricultural protection includingstrobilurins such as azoxystrobin, kresoxim-methyl, pyraclostrobin andtrifloxystrobin; morpholines such as fenpropidine and fenpropimorph;triazoles such as bromuconazole, cyproconazole, difenoconazole,epoxyconazole, flusilazole, ipconazole, metconazole, propiconazole,tebuconazole and triticonazole; pyrimidinone fungicides, benomyl;carbendazim; chlorothalonil; dimethomorph; folpet; mancozeb; maneb;quinoxyfen; validamycin and vinclozolin.

Preferred 4. Preferred compositions comprise a compound of component (a)mixed with cymoxanil.

Preferred 5. Preferred compositions comprise a compound of component (a)mixed with a compound selected from (b1). More preferred is acomposition wherein the compound of (b 1) is mancozeb.

Preferred 6. Preferred compositions comprise a compound of component (a)mixed with a compound selected from (b2). More preferred is acomposition wherein the compound of (b2) is famoxadone.

Of particular note are combinations of Compound 2 or 3 withazoxystrobin, combinations of Compound 2 or 3 with kresoxim-methyl,combinations of Compound 2 or 3 with pyrclostrobin, combinations ofCompound 2 or 3 with trifloxystrobin, combinations of Compound 2 or 3with carbendazim, combinations of Compound 2 or 3 with chlorothalonil,combinations of Compound 2 or 3 with dimethomorph, combinations ofCompound 2 or 3 with folpet, combinations of Compound 2 or 3 withmancozeb, combinations of Compound 2 or 3 with maneb, combinations ofCompound 2 or 3 with quinoxyfen, combinations of Compound 2 or 3 withvalidamycin, combinations of Compound 2 or 3 with vinclozolin, Compound2 or 3 with fenpropidine, combinations of Compound 2 or 3 withfenpropimorph, combinations of Compound 2 or 3 with bromuconazole,combinations of Compound 2 or 3 with cyproconazole, combinations ofCompound 2 or 3 with difenoconazole, combinations of Compound 2 or 3with epoxyconazole, combinations of Compound 2 or 3 with flusilazole,combinations of Compound 2 or 3 with ipconazole, combinations ofCompound 2 or 3 with metconazole, combinations of Compound 2 or 3 withpropiconazole, combinations of Compound 2 or 3 with tebuconazole,combinations of Compound 2 or 3 with triticonazole, combinations ofCompound 2 or 3 with famoxadone, combinations of Compound 2 or 3 withfenamidone, combinations of Compound 2 or 3 with benomyl, combinationsof Compound 2 or 3 with cymoxanil, combinations of Compound 2 or 3 withfosetyl-aluminum, combinations of Compound 2 or 3 with metalaxyl,combinations of Compound 2 or 3 with propineb, combinations of Compound2 or 3 with zineb, combinations of Compound 2 or 3 with copper sulfate,combinations of Compound 2 or 3 with copper hydroxide, combinations ofCompound 2 or 3 with propamocarb, combinations of Compound 2 or 3 withcyazofamid, combinations of Compound 2 or 3 with zoxamid, combinationsof Compound 2 or 3 with fluazinam and combinations of Compound 2 or 3with iprovalicarb. Compound numbers refer to compounds in Index Table A.

Formulation/Utility

Compositions of this invention will generally be used as a formulationor composition comprising at least one carrier selected fromagriculturally suitable liquid diluents, solid diluents and surfactants.The formulation or composition ingredients are selected to be consistentwith the physical properties of the active ingredient, mode ofapplication and environmental factors such as soil type, moisture andtemperature. Useful formulations include liquids such as solutions(including emulsifiable concentrates), suspensions, emulsions (includingmicroemulsions and/or suspoemulsions) and the like which optionally canbe thickened into gels. Useful formulations further include solids suchas dusts, powders, granules, pellets, tablets, films, and the like whichcan be water-dispersible (“wettable”) or water-soluble. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. Sprayableformulations can be extended in suitable media and used at spray volumesfrom about one to several hundred liters per hectare. High-strengthcompositions are primarily used as intermediates for furtherformulation.

The formulations will typically contain effective amounts (e.g. from0.01-99.99 weight percent) of active ingredients together with diluentand/or surfactant within the following approximate ranges which add upto 100 percent by weight. Weight Percent Active Ingredients DiluentSurfactant Water-Dispersible and  5-90  0-94  1-15 Water-solubleGranules, Tablets and Powders. Suspensions, Emulsions,  5-50 40-95  0-25Solutions (including Emulsifiable Concentrates) Dusts  1-25 70-99 0-5Granules and Pellets 0.01-99      5-99.99  0-15 High StrengthCompositions 90-99  0-10 0-2

Typical solid diluents are described in Watkins, et al., Handbook ofInsecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books,Caldwell, N.J. Typical liquid diluents are described in Marsden,Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 'sDetergents and Emulsifiers Annual, Allured Publ, Corp., Ridgewood, N.J.,as well as Sisely and Wood, Encyclopedia of Surface Active Agents,Chemical Publ. Co., Inc., New York, 1964, list surfactants andrecommended uses. All formulations can contain minor amounts ofadditives to reduce foam, caking, corrosion, microbiological growth andthe like, or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols,polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acidesters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzenesulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates,naphthalene sulfonate formaldehyde condensates, polycarboxylates, andpolyoxyethylene/polyoxypropylene block copolymers. Solid diluentsinclude, for example, clays such as bentonite, montmorillonite,attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth,urea, calcium carbonate, sodium carbonate and bicarbonate, and sodiumsulfate. Liquid diluents include, for example, water,N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethyleneglycol, polypropylene glycol, paraffins, alkylbenzenes,alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn,peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters,ketones such as cyclohexanone, 2-heptanone, isophorone and4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol,cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared bysimply mixing the ingredients. Dusts and powders can be prepared byblending and, usually, grinding as in a hammer mill or fluid-energymill. Suspensions are usually prepared by wet-milling; see, for example,U.S. Pat. No. 3,060,084. Preferred suspension concentrates include thosecontaining, in addition to the active ingredient, from 5 to 20% nonionicsurfactant (for example, polyethoxylated fatty alcohols) optionallycombined with 50-65% liquid diluents and up to 5% anionic surfactants.Granules and pellets can be prepared by spraying the active materialupon preformed granular carriers or by agglomeration techniques. SeeBrowning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp147-48, Perry 's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, NewYork, 1963, pages 8-57 and following, and WO 91/13546. Pellets can beprepared as described in U.S. Pat. No. 4,172,714. Water-dispersible andwater-soluble granules can be prepared as taught in U.S. Pat. Nos.4,144,050, 3,920,442 and DE 3,246,493. Tablets can be prepared as taughtin U.S. Pat. Nos. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Filmscan be prepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see U.S. Pat.No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples10-41; U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166,167 and 169-182; U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col.5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, JohnWiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., WeedControl Handbook, 8th Ed., Blackwell Scientific Publications, Oxford,1989.

In the following Examples, all percentages are by weight and allformulations are prepared in conventional ways. Without fartherelaboration, it is believed that one skilled in the art using thepreceding description can utilize the present invention to its fullestextent. The following Examples are, therefore, to be construed as merelyillustrative, and not limiting of the disclosure in any way whatsoever.Percentages are by weight except where otherwise indicated.

EXAMPLE A

Wettable Powder Active ingredients 65.0% dodecylphenol polyethyleneglycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate6.0% montmorillonite (calcined) 23.0%

EXAMPLE B

Granule Active ingredients 10.0% attapulgite granules (low volatilematter, 90.0% 0.71/0.30 mm; U.S.S. No. 25-50 sieves)

EXAMPLE C

Extruded Pellet Active ingredients 25.0% anhydrous sodium sulfate 10.0%crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0%calcium/magnesium bentonite 59.0%

EXAMPLE D

Emulsifiable Concentrate Active ingredients 20.0% blend of oil solublesulfonates 10.0% and polyoxyethylene ethers isophorone 70.0%

EXAMPLE E

Suspension Concentrate Active ingredients 20.0% polyethoxylated fattyalcohol nonionic surfactant 15.0% ester derivative of montan wax 3.0%calcium lignosulfonate anionic surfactant 2.0%polyethoxylated/polypropoxylated polyglycol block copolymer surfactant1.0% propylene glycol diluent 6.4% poly(dimethylsiloxane) antifoam agent0.6% antimicrobial agent 0.1% water diluent 51.9%

The formulation ingredients are mixed together as a syrup, the activeingredients are added and the mixture is homogenized in a blender. Theresulting slurry is then wet-milled to form a suspension concentrate.

Compositions of this invention can also be mixed with one or more otherinsecticides, nematocides, bactericides, acaricides, growth regulators,chemosterilants, semiochemicals, repellents, attractants, pheromones,feeding stimulants or other biologically active compounds to form amulti-component pesticide giving an even broader spectrum ofagricultural protection. Examples of such agricultural protectants withwhich compositions of this invention can be formulated are: insecticidessuch as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin,carbofuran, chlorfenapyr, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin,beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin,diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate,fenoxycarb, fenpropathrin, fenvalerate, fipronil, flucythrinate,tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion,metaldehyde, methamidophos, methidathion, methomyl, methoprene,methoxychlor, methyl7-chloro-2,5-dihydro-2-[[N(tethoxycarbonyl)-N-[4-(trifluoromethoxy)phenyl]amino]carbonyl]indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylate(indoxacarb), monocrotophos, oxamyl, parathion, parathion-methyl,permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb,profenofos, rotenone, sulprofos, tebufenozide, tefluthrin, terbufos,tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon andtriflumuron; bactericides such as streptomycin; acaricides such asamitraz, chinomethionat, chlorobenzilate; cyhexatin, dicofol,dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin,fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad;nematocides such as aldoxycarb and fenamiphos; and biological agentssuch as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin,baculovirus, and entomopathogenic bacteria, virus and fungi. The weightratios of these various mixing partners to compounds of Formula I ofthis invention typically are between 100:1 and 1:100, preferably between30:1 and 1:30, more preferably between 10:1 and 1:10 and most preferablybetween 4:1 and 1:4.

The compositions of this invention are useful as plant disease controlagents. The present invention therefore further comprises a method forcontrolling plant diseases caused by fungal plant pathogens comprisingapplying to the plant or portion thereof to be protected, or to theplant seed or seedling to be protected, an effective amount of acomposition of the invention. The compositions of this invention providecontrol of diseases caused by a broad spectrum of fungal plant pathogensin the Basidiomnycete, Ascomycete, Oomycete and Deuteromycete classes.They are effective in controlling a broad spectrum of plant diseases,particularly foliar pathogens of ornamental, vegetable, field, cereal,and fruit crops. These pathogens include Plasmopara viticola,Phytophthora infestans, Peronospora tabacina, Pseudoperonosporacubensis, Pythium aphanidernatum, Alternaria brassicae, Septorianodorum, Septoria tritici, Cercosporidium personatum, Cercosporaarachidicola, Pseudocercosporella heipotrichoides, Cercospora beticola,Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaeraleucotricha, Venturia inaequalis, Erysiphe graminis, Uncinula necatur,Puccinia recondita, Puccinia graminis, Hentileia vastatrix, Pucciniastriiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerothecafuliginea, Fusariumn oxysporum, Verticillium dahliae, Pythiumnaphanidermatum, Phytophthora mnegaspermna, Sclerotinia sclerotiorurn,Sclerotium rolfsii, Erysiphe polygoni, Pyrenophora teres, Gaeumannomycesgraminis, Rynchosporium secalis, Fusarium roseum, Bremia lactucae andother generea and species closely related to these pathogens. Thecompositions of the invention are especially effective in controllingPlasmopara viticola on grapes and Phytophthora infestans on potatoes andtomatoes.

Plant disease control is ordinarily accomplished by applying aneffective amount of a compound of this invention either pre- orpost-infection, to the portion of the plant to be protected such as theroots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media(soil or sand) in which the plants to be protected are growing. Thecompounds can also be applied to the seed to protect the seed andseedling.

Rates of application for these compounds can be influenced by manyfactors of the environment and should be determined under actual useconditions. Foliage can normally be protected when treated at a rate offrom less than 1 g/ha to 5,000 g/ha of active ingredient. Seed andseedlings can normally be protected when seed is treated at a rate offrom 0.1 to 10 g per kilogram of seed.

The following TESTS demonstrate the control efficacy of compositions ofthis invention on specific pathogens. The pathogen control protectionafforded by the compositions is not limited, however, to these species.See Index Tables A-B for compound descriptions for compounds used in theTESTS. The following abbreviations are used in the Index Tables thatfollow: Me is methyl and OMe is methoxy. The abbreviation “Ex.” standsfor “Example” and is followed by a number indicating in which examplethe compound is prepared. INDEX TABLE A

Compound Number R¹ R² (R⁵)_(m) (R⁶)_(p) m.p. (° C.) 1 (Ex. 2) H CH₃3,5-di-Cl 2,4-di-Cl * racemic 2 (Ex. 1) H CH₃ 3-Cl-5-Br 2,4-di-Cl *racemic 3 H CH₃ 3-Cl-5-I 2,4-di-Cl * 4 H H 3,5-Cl₂ 2,4-di-Cl * 5 H CH₃3-Cl-5-F 2,4-di-Cl * 6 H H 3-Br-5-Cl 2,4-di-Cl * 7 H CH₃ 3,5-di-Br2,4-di-Cl * 8 H H 3-I-5-Cl 2,4-di-Cl * 9 H H 3-Cl-5-Br 2,4-di-Cl * 10 HCH₃ 3,5-di-Me 2,4-di-Cl * 11 H CH₃ 3-Cl-5-OCF₂H 2,4-di-Cl * 12 H H3-Cl-5-I 2,4-di-Cl * 13 H CH₃ 3-Cl-5-Br 2,4-di-Cl-6-Me * 14 H H3-Cl-5-Br 2,4-di-Cl-6-Me * 15 H CH₃ 3-Cl-5-I 2,4-di-Cl-6-Me * 16 H H3-Cl-5-I 2,4-di-Cl-6-Me * 17 H H 3,5-di-Br 2,4-di-Cl * 18 H H 3,5-di-Br2,4-di-Cl-6-Me * 19 H H 3,5-di-Cl 2,4-di-Cl-6-Me * 20 H CH₃ 3,5-di-Cl2,4-di-Cl-6-Me * 21 H CH₃ 3-Cl-5-OMe 2,4-di-Cl-6-Me * 22 H CH₃3-Cl-5-OMe 2,4-di-Cl * 23 H CH₃ 3-l-5-Br 2,4-di-Cl * 24 H H 3-Cl-5-Br2-Cl-4-I * 25 H CH₃ 3-Cl-5-Br 2-Cl-4-I * 26 H H 3,5-Cl₂ 2-Cl-4-I * 27 HCH₃ 3,5-Cl₂ 2-Cl-4-I * 28 H CH₃ 3-Cl-5-Br 2-Cl-4-Br * 29 H CH₃ 3-Cl-5-Br2-Br-4-Me * 30 H CH₃ 3,5-di-Br 2-Cl-4-I * 31 H CH₃ 3,5-di-Br 2-F-4-I *32 H CH₃ 3,5-di-Br 2,4-di-Cl-6-Me * 33 H CH₃ 3-Cl-5-Br 2-F-4-I * 34 HCH₃ 3-Br-5-Cl 2,4-di-Cl * 35 H H 3-Br-5-I 2,4-di-Cl * 36 H CH₃ 3-Br-5-I2,4-di-Cl * 37 H CH₃ 3-Cl-5-Br 2-F-4-Br * 38 H CH₃ 3,5-di-Cl 2-F-4-Br *39 H CH₃ 3,5-di-Br 2-F-4-Br * 40 H H 3-Br-5-Cl 2,4-di-Cl-6-Me * 41 H CH₃3-Br-5-Cl 2,4-di-Cl-6-Me * 42 H H 3-Br-5-I 2,4-di-Cl-6-Me * 43 H CH₃3-Br-5-I 2,4-di-Cl-6-Me **See index Table B for ¹H NMR data.

INDEX TABLE B Cmpd No. ¹H NMR Data(300 mHz; CDCl₃ solution unlessindicated otherwise)^(a) 1 δ 1.58(d, 3H, J is 6.6Hz), 5.7-5.8(m, 1H),7.4(m, 2H), 7.77(m, 1H), 8.35(m, 1H), 8.40(m, 1H). 2 δ 1.59(d, 3H, J is6.6Hz), 5.75(m, 1H), 7.3(bs, 1H), 7.34(d, 1H, J is 5.2Hz), 7.91(d, 1H, Jis 1.9Hz), 8.33(d, 1H, J is 5.4Hz), 8.49(d, 1H, J is 1.9Hz). 3 δ 1.58(d,3H, J is 6.9Hz), 5.7(m, 1H), 7.35(m, 2H), 8.70(d, 1H, J is 1.9), 8.35(m,1H), 8.61(d, 1H, J is 1.9) 4 δ 4.87(d, 2H, J is 4.3Hz), 7.36(d, 1H, J is5.5Hz), 7.79(d, 1H, J is 2.2Hz), 8.35(d, 1H, J is 5.2), 8.41(d, 1H, J is2.1Hz) 5 δ 1.58(d, 3H, J is 6.6Hz), 5.75(m, 1H), 7.3-7.4(m, 2H), 7.55(m,1H), 8.3(m, 2H). 6 δ 4.84(d, 2H, J is 4.1Hz), 7.36(d, 1H, J is 5.5Hz),7.5(bs, 1H), 7.95(d, 1H, J is 2.0Hz), 8.35 (d, 1H, J is 5.5Hz), 8.44(d,1H, J is 2.0Hz) 7 δ 1.58(d, 3H, J is 6.6Hz), 5.7(m, 1H), 7.3-7.4(m, 2H),8.08(d, 1H, J is 2.1Hz), 8.32(d, 1H, J is 5.2Hz), 8.52(d, 1H, J is2.0Hz) 8 δ 4.78(d, 2H, J is 4.2Hz), 7.36(d, 1H, J is 5.3Hz), 7.5(bs,1H), 8.18(d, 1H, J is 2.1Hz), 8.35 (d, 1H, J is 5.3Hz), 8.45(d, 1H, J is2.2Hz) 9 δ 4.84(d, 2H, J is 4.3Hz), 7.36(d, 1H, J is 5.3Hz), 7.4(bs,1H), 7.93(d, 1H, J is 2.2Hz), 8.35 (d, 1H, J is 5.3Hz), 8.50(d, 1H, J is2.1Hz) 10 δ 1.53(d, 3H, J is 5.6Hz), 2.29(s, 3H), 2.39(s, 3H), 5.45(m,1H), 7.32(m, 2H), 7.7(bd, 1H,) 8.16(m, 1H), 8.31(d, 1H, Jis 5.3Hz) 11 δ1.58(d, 3H, J is 6.6Hz), 5.75(m 1H), 6.57(t, 1H, J is 71.8Hz),7.3-7.4(m, 2H), 7.60(d, 1H, J is 1.7Hz), 8.33(m 2H) 12 δ 4.84(d, 2H, Jis 4.3Hz), 7.36(d, 1H, J is 5.5Hz), 7.4(bs, 1H), 8.07(d, 1H, J is1.7Hz), 8.35 (m, 2H), 8.64(d, 1H, J is 1.5Hz) 13 δ 1.57(d, 3H, J is6.5Hz), 2.55(s, 3H), 5.7(m, 1H), 7.18(s, 1H), 7.3(bd, 1H), 7.9(d, 1H, Jis 2.0Hz), 8.48(d, 1H, J is 1.8Hz) 14 δ 2.58(s, 3H), 4.83(d, 2H, J is4.3Hz), 7.21(s, 1H), 7.4(bs, 1H), 7.92(d, 1H, J is 2.1Hz), 8.49(d, 1H, Jis 1.8Hz) 15 δ 1.57(d, 3H, J is 7.2Hz), 2.55(s, 3H), 5.7(m, 1H), 7.18(s,1H), 7.3(bd, 1H, J is 8.2Hz), 8.06(d, 1H, J is 1.7Hz), 8.61(d, 1H, J is1.7Hz) 16 δ 2.56(s, 3H), 4.82(d, 2H, J is 4.1Hz), 7.21(s, 1H), 7.4(bs,1H), 8.07(d, 1H, J is 1.9Hz), 8.62(d, 1H, J is 1.6Hz) 17 δ 4.82(d, 2H, Jis 4.3Hz), 7.36(d, 1H, J is 5.5Hz), 7.47(bs, 1H), 8.09(d, 1H, J is2.0Hz), 8.35(d, 1H, J is 5.5Hz), 8.53(d, 1H, J is 2.0Hz) 18 δ 2.56(s,3H), 4.80(d, 2H, J is 4.1Hz), 7.21(s, 1H), 7.41(bs, 1H), 8.09(d, 1H, Jis 2.1Hz), 8.53(d, 1H, J is 1.9Hz) 19 δ 2.56(s, 3H), 4.85(d, 2H, J is4.3Hz), 7.21(s, 1H), 7.40(bs, 1H), 7.78(d, 1H, J is 2.1Hz), 8.40(d, 1H,J is 2.0Hz) 20 δ 1.57(d, 3H, J is 6.6Hz), 2.55(5, 3H), 5.7(m, 1H),7.19(s, 1H), 7.30(bd, 1H), 7.76(d, 1H, J is 2.0Hz), 8.39(d, 1H, J is2.1Hz) 21 δ 1.56(d, 3H, J is 7.4Hz), 2.54(s, 3H), 3.86(s, 3H), 5.7(m,1H), 7.18(s, 1H), 7.24(m, 1H), 7.4(bd, 1H), 8.12(d, 1H, J is 2.6Hz) 22 δ1.57(d, 3H, is 6.6Hz), 3.87(s, 3H), 5.7(m, 1H), 7.27(m, 1H), 7.33(d, 1H,J is 5.4Hz), 7.45(bd, 1H), 8.12(d, 1H, J is 2.6Hz), 8.32(d, 1H, J is5.2Hz) 23 δ 1.58(d, 3H, J is 6.6Hz), 5.7(m, 1H), 7.35(d, 1H, J is5.5Hz), 7.35(bs, 1H), 8.24(d, 1H, J is 1.6Hz), 8.33(6, 1H, J is 5.4Hz),8.64(d, 1H, J is 1.7Hz) 24 δ 4.84(d, 2H, J is 4.3Hz), 7.4(bs, 1H),7.75(d, 1H, J is 5.2Hz), 7.92(d, 1H, J is 1.9Hz), 8.04 (d, 1H, J is5.2Hz), 8.50(d, 1H, J is 2.0Hz) 25 δ 1.60(d, 3H, J is 6.6Hz), 5.7(m,1H), 7.3(bd, 1H), 7.73(d, 1H, J is 5.3Hz), 7.91(d, 1H, J is 2.0Hz),8.03(d, 1H, J is 5.1Hz), 8.50(d, 1H, J is 1.9Hz) 26 δ 4.86(d, 2H, J is4.3Hz), 7.46(bs, 1H), 7.75(d, 1H, J is 5.2Hz), 7.79(d, 1H, J is 2.1Hz),8.04(d, 1H, J is 5.3Hz), 8.41(d, 1H, J is 2.0Hz) 27 δ 1.6(d, 3H), 5.7(m,1H), 7.4(bs, 1H), 7.7(m 1H), 7.8(m, 1H) 8.01(s, 1H), 8.40(s, 1H) 28 δ1.59(d, 3H, J is 5.8Hz), 5.7(m, 1H), 7.3 bs, 1H), 7.5(m, 1H), 7.9(m,1H), 8.2(m, 1H), 8.45(m, 1H) 29 δ 1.58(d, 3H, J is 6.8Hz), 2.36(s, 3H),5.7(m 1H), 7.13(d, 1H, J is 5.0Hz), 7.2(bd, 1H), 7.91(d, 1H, J is1.9Hz), 8.25(d, 1H, J is 5.1Hz), 8.48(d, 1H, J is 1.9Hz) 30 δ 1.60(d,3H, J is 6.7Hz), 5.7(m, 1H), 7.3(bs, 1H), 7.73(d, 1H, J is 5.3Hz),8.02(d, 1H, J is 5.0Hz), 8.08(d, 1H, J is 2.1Hz), 8.53(d, 1H, J is1.8Hz) 31 δ 1.59(d, 3H, J is 6.5Hz), 5.7(m, 1H), 7.4(bd, 1H), 7.70(m,1H), 7.89(d, 1H, J 5.2Hz), 8.08 (d, 1H, J is 2.0Hz), 8.53(d, 1H, J is1.8Hz) 32 δ 1.58(d, 3H, J is 6.6Hz), 2.55(s, 3H), 5.7(m, 1H), 7.18(s,1H), 7.29(bd, 1H), 8.07(d, 1H, J is 1.9Hz), 8.51(d, 1H, J is 2.1Hz) 33 δ1.58(d, 3H, J is 6.6Hz), 5.7(m, 1H), 7.4(bd, 1H), 7.70(d of d, 1H, J is0.9, 5.2Hz), 7.91 (m, 2H), 8.50(d, 1H, J is 2.1Hz) 34 δ: 1.58(d,J=6.6Hz, 3H), 5.72(m, 3=6.6Hz, 1H), 7.33(d, J=5.2Hz, 1H), 7.38(broad s,1H), 7.93(d, 2.1Hz, 1H), 8.33(d, J=5.2Hz, 1H), 8.42(d, J=2.1Hz, 1H). 35δ: 4.80(d, J=5Hz, 2H), 7.35(d, J=5.5Hz, 1H), 7.49(broad S, 1H), 8.24(d,J=1.9Hz, 1H), 8.35(d, J=5.5Hz, 1H), 8.66(d, J=1.9Hz, 1H). 36 δ: 1.58(d,J=6.6Hz, 3H), 5.69(m, J=6.6Hz, 1H), 7.33(d, J=5.2Hz, 1H), 7.36(broad s,1H), 8.24(d, 1.7Hz, 1H), 8.33(d, J=5.2Hz, 1H), 8.64(d, J=1.7Hz, 1H). 37δ: 1.57(d, 3H, J is 6.5Hz), 5.7(m, 1H), 7.4(bd, 1H), 7.47(m, 1H),7.91(d, 1H, J is 2.0Hz), 8.09(m, 1H), 8.49(d 1H, J is 2.1Hz) 38 δ:1.58(d, 3H, J is 6.5Hz), 5.7(m, 1H), 7.4(bd, 1H), 7.46(d, 1H, J is5.5Hz), 7.77(d, 1H, 3 is 2.0Hz), 8.09(d, 1H, J is 5.4Hz), 8.40(d, 1H, Jis 2.1Hz) 39 δ: 1.58(d, 3H, J is 6.6Hz), 5.65(m, 1H), 7.4(bd, 1H),7.46(m, 1H), 8.1(m, 2H), 8.52(d, 1H, J is 2.1Hz) 40 δ: 2.55(s, 3H),4.81(d, J=4.5Hz, 2H), 7.20(s, 1H), 7.51(broad S, 1H), 7.94(d, J=2.1Hz,1H), 8.42(d, J=2.1Hz, 1H). 41 δ: 1.57(d, J=6.7Hz, 3H), 2.54(s, 3H),5.73(m, J=6.7Hz, 1H), 7.18(s, 1H), 7.33(broad d, 1H), 7.93(d, 2.1Hz,1H), 8.41(d, J=2.1Hz, 1H). 42 δ: 2.55(s, 3H), 4.78(d, J=4.3Hz, 2H),7.20(s, 1H), 7.46(broad S, 1H), 8.23(d, J=1.8Hz, 1H), 8.65(d, J=1.8Hz,1H). 43 δ: 1.57(d, J=6.5Hz, 3H), 2.54(s, 3H), 5.68(m, J=6.5Hz, 1H),7.18(s, 1H), 7.34(broad d, 1H), 8.23(d, 1.8Hz, 1H), 8.64(d, J=1.8Hz,1H).^(a) ¹H NMR data are in ppm downfield from tetramethylsilane. Couplingsare designated by(s)-singlet,(d)-doublet,(t)-triplet,(q)-quartet,(m)-multiplet,(dd)-doublet ofdoublets,(dt)-doublet of triplets, (br s)-broad singlet.

Biological Examples Of The Invention

General protocol for preparing test suspensions: Test compounds arefirst dissolved in acetone in an amount equal to 3% of the final volumeand then suspended at the desired concentration (in ppm) in acetone andpurified water (50/50 mix) containing 250 ppm of the surfactant Trem®014 (polyhydric alcohol esters). The resulting test suspensions are thenused in the following tests. Spraying a 200 ppm test suspension to thepoint of run-off on the tests plants is the equivalent of a rate of 500g/ha.

Test A

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporedust of Erysiphe graminis f. sp. tritici, (the causal agent of wheatpowdery mildew) and incubated in a growth chamber at 20° C. for 7 days,after which disease ratings were made.

Test B

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Puccinia recondita (the causal agent of wheat leaf rust)and incubated in a saturated atmosphere at 20° C. for 24 h, and thenmoved to a growth chamber at 20° C. for 6 days, after which diseaseratings were made.

Test C

The test suspension was sprayed to the point of run-off on riceseedlings. The following day the seedlings were inoculated with a sporesuspension of Pyricularia oryzae (the causal agent of rice blast) andincubated in a saturated atmosphere at 27° C. for 24 h, and then movedto a growth chamber at 30° C. for 5 days, after which disease ratingswere made.

Test D

The test suspension was sprayed to the point of run-off on tomato (orpotato) seedlings. The following day the seedlings were inoculated witha spore suspension of Phytophthora infestans (the causal agent of potatoand tomato late blight) and incubated in a saturated atmosphere at 20°C. for 24 h, and then moved to a growth chamber at 20° C. for 5 days,after which disease ratings were made.

Test E

The test suspension was sprayed to the point of run-off on grapeseedlings. The following day the seedlings were inoculated with a sporesuspension of Plasmopara viticola (the causal agent of grape downymildew) and incubated in a saturated atmosphere at 20° C. for 24 h,moved to a growth chamber at 20° C. for 6 days, and then incubated in asaturated atmosphere at 20° C. for 24 h, after which disease ratingswere made.

Test F

Potato seedlings are inoculated with a spore suspension of Phytophthorainfestans (the causal agent of potato and tomato late blight) andincubated in a saturated atmosphere at 20° C. for 24 h. The next day,test suspension is sprayed to the point of run-off and the treatedplants are moved to a growth chamber at 20° C. for 5 days, after whichdisease ratings are made.

Test G

Grape seedlings are inoculated with a spore suspension of Plasmoparaviticola (the causal agent of grape downy mildew) and incubated in asaturated atmosphere at 20° C. for 24 h. The next day, test suspensionis sprayed to the point of run-off and the treated plants are moved to agrowth chamber at 20° C. for 6 days, and then incubated in a saturatedatmosphere at 20° C. for 24 h, after which disease ratings are made.

Results for Tests A-G are given in Table A. In the table, a rating of100 indicates 100% disease control and a rating of 0 indicates nodisease control (relative to the controls) A dash (−) indicates no testresults. TABLE A Cmpd Test No. A Test B Test C Test D Test E Test F#Test G 1 0 38 0 100  99 87 100 2 0 19 0 100 100 93 100 3 0 19 — 100  9588 100 4 0 9 — 100  70 100 100 5 0 0 — 100  70 100  99 6 0 0 — 100  70100  99 7 0 45 — 100 100 100 100 8 0 0 — 100 100 100  36 9 0 9 — 100  8899  99 10 0 0 —  99  57 0  0 11 0 0 — 100 100 93 100 12 0 0 — 100  59 98 63 13 0 68 — 100 100 100 100 14 0 41 — 100 100 98 100 15 0 0 — 100 10070 100 16 0 32 — 100 100 83  95 17 0 — — 100  99 73  98 18 0 — — 100 10077 100 19 0 — —  99 100 0 100 20 0 — — 100 100 53 100 21 0 — —  99 10053  77 22 0 — — 100 100 98  94 23 0 — — 100 100 98  96 24 0 — — 100 1000  84 25 0 — — 100 100 0  72 26 0 — — 100  81 0  99 27 0 — — 100 100 0100 28 0 — —  99 100 100 100 29 0 — —  99 100 57  94 30 0 — — 100 100 44 93 31 0 — — 100 100 79 100 32 0 — — 100 100 82  99 33 0 — — 100 100 100100 34 0 — — 100 100 99 100 35 0 — —  100#  99* 96  50* 36 0 — —  100# 100* 92  92* 37 0 — — 100 100 100 100 38 0 — — 100 100 100 100 39 0 — —100 100 100 100 40 0 — — 100 100 95  99 41 0 — — 100 100 97 100 42 0 — —100 100 93 100 43 0 — — 100 100 90 100#100 g/ha on potato seedlings*rate 100 g/ha

Synergism has been described as “the cooperative action of twocomponents (e.g. component (a) and component (b)) of a mixture, suchthat the total effect is greater or more prolonged than the sum of theeffects of the two (or more) taken independently” (see Tames, P. M. L.,Neth. J. Plant Pathology, 1964, 70, 73-80). It is found thatcompositions containing the compound of Formula I and fungicides with adifferent mode of action exhibit synergistic effects.

The presence of a synergistic effect between two active ingredients isestablished with the aid of the Colby equation (see Colby, S. R. InCalculating Synergistic and Antagonistic Responses of HerbicideCombinations, Weeds, 1967, 15, 20-22):$p = {A + B - \left\lbrack \frac{A \times B}{100} \right\rbrack}$

Using the methods of Colby, the presence of a synergistic interactionbetween two active ingredients is established by first calculating thepredicted activity, p, of the mixture based on activities of the twocomponents applied alone. If p is lower than the experimentallyestablished effect, synergism has occurred. In the equation above, A isthe fungicidal activity in percentage control of one component appliedalone at rate x. The B term is the fungicidal activity in percentagecontrol of the second component applied at rate y. The equationestimates p, the fungicidal activity of the mixture of A at rate x withB at rate y if their effects are strictly additive and no interactionhas occurred.

The following TESTS can be used to demonstrate the control efficacy ofcompositions of this invention on specific pathogens. The pathogencontrol protection afforded by the compounds is not limited, however, tothese species.

Test suspensions comprising a single active ingredient are sprayed todemonstrate the control efficacy of the active ingredient individually.To demonstrate the control efficacy of a combination, (a) the activeingredients can be combined in the appropriate amounts in a single testsuspension, (b) stock solutions of individual active ingredients can beprepared and then combined in the appropriate ratio, and diluted to thefinal desired concentration to form a test suspension or (c) testsuspensions comprising single active ingredients can be sprayedsequentially in the desired ratio.

Composition 1

Ingredients Wt. % Compound 2 Technical Material 20 Polyethoxylatedstearyl alcohol 15 Montan wax ester 3 Desugared calcium lignosulfate 2Polyoxypropylene-polyoxyethylene block copolymer 1 Propylene Glycol 6.4Polyorganosiloxanes + emulsifying agent 0.6 19%(1,2-benzisothiazolin-3-one) in aqueous dipropylene glycol 0.1 Water51.9

Composition 2

Ingredients Wt. % Compound 3 Technical Material 20 Polyethoxylatedstearyl alcohol 15 Montan wax ester 3 Desugared calcium lignosulfate 2Polyoxypropylene-polyoxyethylene block copolymer 1 Propylene Glycol 6.4Polyorganosiloxanes + emulsifying agent 0.6 19%(1,2-benzisothiazolin-3-one) in aqueous dipropylene glycol 0.1 Water51.9

Composition 4

Ingredients Wt. % Famoxadone Technical Material 51.7 Sodium lignosulfate36.0 Sodium alkylnaphthalene sulfonate 2.0 Polyvinyl pyrrolidone 4.0Polyoxypropylene-polyoxyethylene 3.0 block copolymer Sodiumdodecylbenzene sulfonate 3.0 Fluoroalkyl acid mixture 0.3

Composition 5

Ingredients Wt. % Cymoxanil Technical Material 61.9 Sodiumalkylnaphthalene sulfonate 5.0 formaldehyde condensate Sodiumalkylnaphthalene sulfonate 1.0 Polyvinyl pyrrolidone 4.0 Monosodiumphosphate 4.0 Fumaric acid 1.0 Fumed silica 1.0 Sodium 0.2 Sugar 14.0Sodium lignosulfate 7.9

Test compositions were first mixed with purified water containing 250ppm of the surfactant Trem® 014 (polyhydric alcohol esters). Theresulting test suspensions were then used in the following tests. Testsuspensions were sprayed to the point of run-off on the test plants atthe equivalent rates of 5, 10, 20, 25, 50 or 100 g/ha of the activeingredient. Spraying a 40 ppm test suspension to the point of nm-off onthe test plants is the equivalent of a rate of 100 g/ha. The tests werereplicated three times and the results reported as the average of thethree replicates.

Test H (Preventive Control of Phytophthora infestans)

The test suspensions were sprayed to the point of run-off on Potatoseedlings. The following day the seedlings were inoculated with a sporesuspension of Phytophthora infestans (the causal agent of tomato andpotato late blight) and incubated in a saturated atmosphere at 20° C.for 24 h, and then moved to a growth chamber at 20° C. for 5 days, afterwhich disease ratings were made.

Test I (Curative Control of Phytophthora infestans)

Potato seedlings were inoculated with a spore suspension of Phytophthorainfestans (the causal agent of tomato and potato late blight) 24 hoursprior to application and incubated in a saturated atmosphere at 20° C.for 24 h. The test suspensions were then sprayed to the point of run-offon the potato seedlings. The following day the seedlings were moved to agrowth chamber at 20° C. for 5 days, after which disease ratings weremade.

Test J (Extended Preventive Control of Phytophthora infestans)

The test suspensions was sprayed to the point of run-off on potatoseedlings. Six days later, the seedlings were inoculated with a sporesuspension of Phytophthora infestans (the causal agent of tomato andpotato late blight) and incubated in a saturated atmosphere at 20° C.for 24 h, and then moved to a growth chamber at 20° C. for 5 days, afterwhich disease ratings were made.

Results for Tests H-J are given in Table B. In the table, a rating of100 indicates 100% disease control and a rating of 0 indicates nodisease control (relative to the controls). Columns labeled Avgindicates the average of three replications. Columns labeled Expindicate the expected value for each treatment mixture using the Colbyequation. Tests demonstrating control greater than expected areindicated with *. TABLE A Composition Test H Test I Test J Number RateAvg Exp Avg Exp Avg Exp 1 5  0 xx 0 xx  0 xx 1 10  72 xx 0 xx 21 xx 1 20 97 xx 0 xx 47 xx 2 5  0 xx 0 xx  0 xx 2 10  47 xx 0 xx 32 xx 2 20 100xx 0 xx 82 xx 3 25 100 xx 0 xx  0 xx 3 50 100 xx 0 xx  0 xx 3 100 100 xx0 xx  0 xx 4 25  0 xx 0 xx  0 xx 4 50  0 xx 0 xx  0 xx 4 100  32 xx 0 xx 0 xx 1 + 3  5 + 25 100 100 0 0  9 0 1 + 3 10 + 50 100 100 0 0  9 21 1 +3  20 + 100  98 100 0 0  76* 47 1 + 4  5 + 25  0 0 0 0  21* 0 1 + 4 10 +50  32 72 9 0  77* 21 1 + 4  20 + 100 100 98  29* 0 65* 47 2 + 3  5 + 25100 100 0 0  69* 0 2 + 3 10 + 50 100 100 0 0  72* 32 2 + 3  20 + 100 100100 0 0  99* 82 2 + 4  5 + 25  24 0 0 0  9 0 2 + 4 10 + 50  98* 47 0 0 75* 32 2 + 4  20 + 100 100 100 9 0  99* 82

Based on the description of synergism developed by Colby, compositionsof the present invention are illustrated to be synergistically useful.Moreover, compositions comprising components (a) and (b) alone can beconveniently mixed with an optional diluent prior to applying to thecrop to be protected. Accordingly, this invention provides an improvedmethod of combating fungi, particularly fungi of the class Oomycetessuch as Phytophthora spp. and Plasmopara spp., in crops, especiallypotatoes, grapes and tomatoes.

1. A composition for controlling plant diseases caused by fungal plant pathogens comprising: (a) at least one compound of Formula I, N-oxides and agriculturally suitable salts thereof

 wherein R¹ and R² are each independently H or C₁-C₆ alkyl; each R⁵ is independently C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkyl, C₃-C₆ halocycloalkyl, halogen, CN, CO₂H, CONH₂, NO₂, hydroxy, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl, C₁-C₄ haloalkylsulfonyl, C₁-C₄ alkylamino, C₂-C₈ dialkylamino, C₃-C₆ cycloalkylamino, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl, C₃-C₈ dialkylaminocarbonyl or C₃-C₆ trialkylsilyl; each R⁶ is independently C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ halocycloalkyl, halogen, CN, CO₂H, CONH₂, NO₂, hydroxy, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl, C₁-C₄ haloalkylsulfonyl, C₁-C₄ alkylamino, C₂-C₈ dialkylamino, C₃-C₆ cycloalkylamino, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl, C₃-Cg dialkylaminocarbonyl or C₃-C₆ trialkylsilyl; and m and n are independently 1, 2, 3 or 4; and (b) at least one compound selected from the group consisting of (b1) alkylenebis(dithiocarbamate) fungicides; (b2) compounds acting at the bc, complex of the fungal mitochondrial respiratory electron transfer site; (b3) cymoxanil; (b4) compounds acting at the demethylase enzyme of the sterol biosynthesis pathway; (b5) morpholine and piperidine compounds that act on the sterol biosynthesis pathway; (b6) phenylamide fungicides; (b7) pyrimidinone fungicides; (b8) phthalimides; and (b9) fosetyl-aluminum.
 2. The composition of claim 1 wherein the weight ratio of component (b) to component (a) is from 9:1 to 4.5:1.
 3. The composition of claim 2 wherein component (b) is cymoxanil.
 4. The composition of claim 2 wherein component (b) is a compound selected from (b1).
 5. The composition of claim 4 wherein component (b) is mancozeb.
 6. The composition of claim 2 wherein component (b) is a compound selected from (b2).
 7. The composition of claim 6 wherein component (b) is famoxadone.
 8. The composition of claim 1 wherein component (b) comprises at least one compound from each of two different groups selected from (b1), (b2), (b3), (b4), (b5), (b6), (b7), (b8) and (b9).
 9. The composition of claim 8 wherein component (b) comprises at least one compound selected from (b1) and at least one compound selected from (b2), (b3), (b6), (b7), (b8) or (b9); wherein the overall weight ratio of component (b) to component (a) is from 30:1 to 1:30; and wherein the weight ratio of component (b1) to component (a) is from 10:1 to 1:1.
 10. The composition of claim 8 wherein component (b) comprises at least one compound selected from (b2) and at least one compound selected from (b1), (b3), (b6), (b7), (b8) or (b9); wherein the overall weight ratio of component (b) to component (a) is from 30:1 to 1:30; and wherein the weight ratio of component (b2) to component (a) is from 10:1 to 1:1.
 11. The composition of claim 8 wherein component (b) comprises cymoxanil and at least one compound selected from (b0), (b2), (b6), (b7), (b8) or (b9); wherein the overall weight ratio of component (b) to component (a) is from 30:1 to 1:30; and wherein the weight ratio of cymoxanil to component (a) is from 10:1 to 1:1.
 12. A method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of a composition of claim
 1. 13. The method of claim 12 wherein the disease to be controlled is caused by the fungal pathogen Phytophthora infestans.
 14. The method of claim 12 wherein the disease to be controlled is caused by the fungal pathogen Plasmopara viticola.
 15. A compound of Formula I, including all geometric and stereoisomers, N-oxides and agriculturally suitable salts thereof:

wherein R¹ and R² are each independently H or C₁-C₆ alkyl; each R⁵ is independently C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ halocycloalkyl, halogen, CN, CO₂H, CONH₂, NO₂, hydroxy, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl, C₁-C₄ haloalkylsulfonyl, C₁-C₄ alkylamino, C₂-C₈ dialkylamino, C₃-C₆ cycloalkylamino, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl, C₃-C₈ dialkylaminocarbonyl or C₃-C₆ trialkylsilyl; each R⁶ is independently C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ halocycloalkyl, halogen, CN, CO₂H, CONH₂, NO₂, hydroxy, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl, C₁-C₄ haloalkylsulfonyl, C₁-C₄ alkylamino, C₂-C₈ dialkylamino, C₃-C₆ cycloalkylamino, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl, C₃-C₈ dialkylaminocarbonyl or C₃-C₆ trialkylsilyl; provided that at least one R⁶ is iodo; and m and n are independently 1, 2, 3 or
 4. 